KR20240016412A - Method for producing polyether-polysiloxane block copolymer composition, polyether-polysiloxane block copolymer composition, and use thereof - Google Patents

Abstract

[Problem] To provide a hydrosilylation reaction process of an (AB)n-type polyether-modified silicone composition that has sufficient quality and consistency even when a low-cost glycol ether compound is used as a raw material. [Solution] Step 1 of mixing raw material components containing at least (a1) alkenyl polyether at both ends and (N+S) specific monovalent carboxylic acid sodium salt solution, Step 2 of removing the solvent component (S) from the system. , and a process of hydrosilylating the raw material components (however, the total amount of component (a1), component (a2), and component (B') in parts by weight: component (B') = 100:40 to 80, component (B') ), a method for producing a composition comprising a polyether-polysiloxane block copolymer (A'), wherein the content of Na ⁺ in component (N) is in the range of 3.8 to 43 wt.ppm), a foam-enhancing composition, and Their use.

Description

Method for producing polyether-polysiloxane block copolymer composition, polyether-polysiloxane block copolymer composition, and use thereof

The present invention relates to an improved hydrosilylation reaction process for preparing a polyether-polysiloxane block copolymer having a specific structure and a polyether-polysiloxane block copolymer-containing composition containing a glycol ether compound. The present invention further relates to a composition containing a polyether-polysiloxane block copolymer with improved foam enhancement properties, comprising a specific amount of sodium salt of a monovalent carboxylic acid. Additionally, the present invention relates to a surfactant containing these compositions and a foam stabilizer for polyurethane foam (including functions as a foam control agent and a foam stabilizer; the same applies hereinafter).

The linear organopolysiloxane-polyether block copolymer obtained by hydrosilylation reaction of (1) organopolysiloxane containing SiH groups at both ends and (2) polyether containing C=C groups at both ends is non-hydrolyzable. It is known as (AB)n-type polyether modified silicone (Patent Documents 1 and 2). These block copolymers were obtained by carrying out a hydrosilylation reaction in a toluene solvent, but because toluene has a high risk of hazards such as its toxicity and flammability, it is usually removed from the product system by stripping treatment under heating or reduced pressure conditions. Similarly, although xylene solutions containing the block copolymer were known and commercialized, they also had the problem of containing flammable and harmful organic solvents.

Patent Document 3 discloses an example using a solvent exchange method in which the copolymer was synthesized in toluene, polypropylene glycol as a diluent was added, and toluene was further removed by stripping, and urethane foam was used as a diluent. Polyols used in prescriptions were also mentioned as being available. In addition, as a comparative example, a commercially available foaming agent using long-chain alkylbenzene as a reaction solvent and diluent was adopted. The solvent exchange method is advantageous in that it not only improves handling by lowering the viscosity of the (AB)n-type polyether-modified silicone foam stabilizer, but also makes urethane foam a low VOC (Volatile Organic Compound), but is also advantageous in terms of foam generation during solvent exchange. The problem lies in the low production efficiency. Although long-chain alkylbenzenes have the advantage of simplifying the manufacturing process of foam stabilizers, they remain in urethane foam and become a source of VOC, and further have the problem of migrating (exuding) from the final product.

Patent Document 4 relates to a method for producing a siloxane-polyoxyalkylene copolymer by performing a hydrosilylation reaction under reduced pressure, and is a (AB)n-type polyether using IPP (isopropyl palmitate) as a reaction solvent and diluent. A modified silicone composition was disclosed. However, ester oils, such as IPP, have the problem of being prone to separation due to poor compatibility with the copolymer, especially at low temperatures, and when included in foam stabilizers, they can cause VOCs and migration from urethane foam. there is.

Patent Document 5 discloses a technology for stably producing non-hydrolyzable (AB)n-type polyether-modified silicone or similar structures, especially high molecular weight copolymers, without causing thickening or gelation. Among these, an example was shown in which the copolymer was synthesized in liquid isoparaffin, and then low-boiling substances such as unreacted substances were distilled off by stripping (however, most of the liquid isoparaffin remained as a diluent for the copolymer). However, liquid isoparaffin, if included in anti-foaming agents, may cause VOCs and migration from urethane foam.

Patent Document 6 is an invention made to solve the problems related to Documents 1 to 5, and includes (A) a non-hydrolyzable (AB)n-type polyether-modified silicone, and (B) a hydrocarbon with a terminal hydrogen having 1 to 8 carbon atoms. A composition containing a specific glycol ether compound substituted by a group and having a secondary alcoholic hydroxyl group at the other end, a method for producing the same, an anti-inflammatory agent containing the same, etc. are disclosed. This component (B) can be used as a reaction solvent and diluent for the production of component (A). In addition, when forming urethane foam, it is incorporated into the urethane resin skeleton due to the reactivity of the hydroxyl group, thereby minimizing the VOC of the foam and stabilizing the foam. There is an advantage in achieving both efficient production of rituals.

Patent Document 7 is a solution to the problem that hydrosilylation of a SiH-containing compound and a compound having an olefinically unsaturated group at the terminal by a chloroplatinic acid catalyst cannot be sufficiently performed because significant side reactions occur in the presence of water or alcohols, It was proposed to carry out the hydrosilylation by coexisting an aqueous buffer solution that maintains the pH of the system at 5 to 7 even in the presence of a strong acid.

Patent Document 8 is a reaction accelerator (or catalytic modifier), RCO ₂ M (wherein M is selected from the group consisting of H, alkali metal, alkaline earth metal, ammonium ion, and tetraalkylphosphonium ion, and R is a carbon atom A branched polyether characterized in that the hydrosilylation reaction of a monoalkenyl polyether having a hydroxyl group at the terminal is carried out without solvent in the presence of a carboxylic acid or carboxylic acid salt represented by a monovalent hydrocarbon group having a number of 2 to 20. A method for producing modified silicon was disclosed. In the examples, 0.02 to 0.5 wt.% of sodium propionate or sodium butyrate was used relative to the monoallyl polyether, but since 85% phosphoric acid water used to neutralize the SiH group-containing polysiloxane was also mixed in the reaction system, The composition of the actual buffer system is complex, and there is no description or suggestion of a buffer system that is easy to use industrially or the effect of using a specific amount of buffer.

Patent Document 9 discloses a process for preparing a general branched polyether-modified silicone surfactant by hydrosilylation reaction in a high boiling point polyol solvent without an olefinically unsaturated group such as dipropylene glycol, and a process comprising the silicone surfactant and the polyol solvent. A mixture was claimed, wherein the polyol content in the mixture was at least 5 wt.% and contained at least 100 ppm of an alkali or alkaline earth metal salt of a C2 to C19 monovalent carboxylic acid as a reaction accelerator. In the test examples in this document, an ethanol solution of chloroplatinic acid was used as a catalyst for hydrosilylation, and as buffering agents, 550 ppm sodium oleate (Example 7), 550 ppm sodium butyrate (Example 8), and 550 ppm for the entire mixture. of potassium acetate (Example 9) was used.

Patent Document 10 is a surfactant composition for flexible polyurethane foam, and claims a mixture containing 99.98 to 90 wt.% of non-hydrolyzable branched polyether-modified silicone suitable for the above application and 0.02 to 10 wt.% of an organic acid salt. In this technology, the addition of the organic acid salt and the manufacturing process of the polyether-modified silicone are independent of each other, the organic acid salt is added to the polyether-modified silicone as a solid or an aqueous solution, and heating to reduce the water content is optional. The obtained surfactant composition is said to have improved the height and breathability of flexible polyurethane foam. The organic acid salts and their addition amounts tested in the examples were sodium dodecylbenzenesulfonate: 0.2-1.6 wt.%, sodium p-toluenesulfonate: 0.4 wt.%, bis-(2, 4, 4-trimethylpentyl)phosphinic acid. Sodium:, potassium oleate: 0.4 wt.%.

Patent Document 11 claims a method for producing a general side-chain polyether-modified silicone by hydrosilylation using a platinum catalyst in an organic solvent, and provides a high-purity monoalkenyl-terminated polyether with suppressed peroxide value and total carbonyl amount. By using it, polyether-modified silicone with low odor is obtained, followed by a water distillation process after the reaction, addition of a predetermined amount of antioxidant, and optionally a buffering agent with a pH of 5.5 to 8 when dissolved in water. It was equipped with additions. In this technique, the addition of the buffering agent is performed after the polyether-modified silicone has been synthesized. In Reference Examples 1 to 4, an IPA solution of chloroplatinic acid was used as a catalyst, and a methanol solution of sodium acetate (100 wt.ppm as sodium acetate for the polyether-modified silicone composition excluding the organic solvent) was used as a buffer.

Patent Document 12 discloses a solvent-free continuous production process by hydrosilylation of a silicone copolymer using a static mixing plug flow reactor. When the hydroxyl group at the end of the polyether is not blocked, it is recommended to use a buffering agent such as a carboxylate, and this salt is dissolved in polyether in advance and then introduced into the reactor: In Example 19, it is added to the polyether. 100 wt.ppm of sodium propionate was used. On the other hand, in Comparative Example 12, completely the same raw materials as in Example 19 were used, two tank-type continuous reactors and one plug flow reactor were connected in this order, and raw materials were continuously supplied and discharged to produce branched-chain poly Ether modified silicone was prepared.

Patent Document 13 discloses a polyorganosiloxane-polyoxyethylene block copolymer [specific (AB)n-type polyether-modified silicone], its production method, and a vesicle composition containing the same. In Examples 1 to 4, a dimethylsiloxane solution of l,3-diethenyl-l,l,3,3-tetramethylsiloxane platinum complex was used as a catalyst, and the reaction was carried out in a xylene solvent in the presence of 484 to 688 ppm of sodium acetate. was performed to prepare the (AB)n-type polyether-modified silicone. In Examples 8 to 11, the same (AB)n-type polyether-modified silicone was prepared by performing a reaction in an IPA solvent using the same catalyst in the presence of 438 to 500 ppm of sodium acetate. These reaction solvents were removed by a stripping operation after completion of the reaction.

In addition, Patent Document 13 discloses a number of reaction solvents that can be used as needed in producing the (AB)n-type polyether-modified silicone, and monoethers of propylene glycol or dipropylene glycol are also included, but selectable solvents The disclosure was limited to a non-limiting example of a solvent. In addition, among these many solvents, there are many solvents that are not practical when used in the production of (AB)n-type polyether-modified silicone because they cause inhibition of the reaction, non-uniformity of the reaction system, side reactions, etc., and the optimal In order to search for solvents, it is necessary for those skilled in the art to conduct extensive experiments to verify the reactivity and stability of these solvents, resulting in a lack of specific skills in selecting a suitable solvent. In particular, (B) a specific glycol ether compound in which the terminal hydrogen is substituted by a hydrocarbon group having 1 to 8 carbon atoms and also has a secondary alcoholic hydroxyl group at the other terminal, (AB) has a structure suitable as a main component of a foam stabilizer for polyurethane foam. Can be used as a solvent and diluent for the synthesis reaction of n-type polyether-modified silicone, thereby improving the industrial production process of the foam stabilizer, and realizing fine cells of urethane foam due to good compatibility between the foam stabilizer and the premix solution. There was nothing written or hinted at about the benefits. Therefore, Patent Document 13 did not provide clear teachings that could be understood by those skilled in the art regarding the invention of Patent Document 6 and its technical benefits.

Patent Document 14 discloses a 1 mol% polyether having at least one terminal unsaturated aliphatic hydrocarbon group and an alkali metal content of less than 50 ppm, and an organohydrogensiloxane having an acid value of less than 0.005 through hydrosilylation reaction. A process for producing polyether modified silicone having a -SiOC- content of less than 100% was disclosed. In all of the experimental examples, the synthesis reaction of a general side-chain polyether-modified silicone was carried out under solvent-free conditions, and 13 ppm of sodium acetate (Comparative Example 4) or 15 ppm of potassium acetate (Comparative Example 5) was added to the reaction system. It was reported that it caused a delay in reaction speed. This technology uses purified raw materials with a low content of ionic impurities on both the siloxane side and the polyether side for hydrosilylation, thereby maintaining excellent reactivity without stagnation in the reaction system continuously, resulting in polyether-modified silicone. It is based on the concept of realizing stable and efficient production. In addition, a large number of usable reaction solvents are disclosed, and monoethers of propylene glycol or dipropylene glycol are also included, but the above-mentioned problems that arise when these are used as a solvent for the synthesis of (AB)n-type polyether-modified silicone There was no mention of the cause at all. Therefore, the technical idea of Patent Document 14 and the present invention are different.

Patent Document 15 discloses a composition containing a general side-chain polyether-modified silicone and something similar to (B) above, a method for producing the same, a foam stabilizer containing the same, etc. In this paragraph 0084, a plurality of options regarding the addition method of a buffering agent such as an alkali metal carboxylic acid salt and the addition thereof are shown for purposes such as suppressing side reactions. In addition, when a polar solvent is used to dissolve the salt, there is a technology that allows removal by stripping before or after the start of the main reaction. However, the types and methods of use of buffering agents remain as non-limiting disclosures, and buffering agents were not used in the Examples/Comparative Examples, so there was no information regarding the appropriate addition amount of the buffering agent component. In addition, it is difficult to guess from Patent Document 15 the above-mentioned unique problems that occur when low-priced raw materials (B) are used as a solvent for synthesis of (AB)n-type polyether-modified silicone (A), and therefore, the best solution is As for the solution, no concrete or specific means were indicated at all.

On the other hand, Patent Documents 1 to 15 teach the use of a buffer containing an alkali metal salt of carboxylic acid in the process of producing (AB)n-type polyether modified silicone, etc. by hydrosilylation reaction, but hydrosilylation For the purpose of improving the reaction process, there is no description or suggestion of specific experimental examples of mixing a specific buffer solution into the raw material system before starting the reaction, then removing the solvent of the buffer and starting the post-reaction, or the technical effects thereof. It wasn't done. In particular, among these documents are "(AB)n-type polyether modified silicone" with a specific structure and "specific glycol ethers in which the terminal hydrogen is replaced by a hydrocarbon group with 1 to 8 carbon atoms and a secondary alcoholic hydroxyl group at the other terminal. Regarding the composition containing “compound” as the main ingredient, the examples and technical effects of the improved hydrosilylation reaction process to solve the quality problems thereof were not described or suggested at all.

In addition, the role or expected effect of the buffer in Patent Documents 1 to 15 is to neutralize acidic substances in the system (thereby suppressing side reactions during production = promoting the main reaction, or suppressing changes over time after production and during product storage). It is based on function. In other words, the weak alkaline buffer in these documents is a literal expression and includes a plurality of buffers, reaction accelerators, catalytic modifiers, and additives for low embrittlement, but the fundamental function of expressing them is neutralization or adjusting the pH of the system, and is specific. Descriptions and suggestions have been made suggesting the discovery of a new function by the present inventors, namely, that when a small amount of sodium salt is present in the composition in a soluble amount, the composition is given a specifically enhanced surface activity ability and foam retention ability. Didn't lose.

Patent Document 1: U.S. Patent Specification No. 3957842 (Japanese Patent Application Publication No. (S) 56-22395) Patent Document 2: US Patent Specification No. 4150048 Patent Document 3: Japanese Patent Publication No. 08-156143 Patent Document 4: U.S. Patent Specification No. 5869727 (Japanese Patent Application Publication No. 11-116670) Patent Document 5: Japanese Patent Publication No. 2006-282820 (Japanese Patent Publication No. 4875314) Patent Document 6: International Publication No. 2016/166979 (US Patent Specification No. 10717872) Patent Document 7: US Patent Specification No. 3398174 Patent Document 8: U.S. Patent Specification No. 4847398 (Japanese Patent Publication No. 5-51619) Patent Document 9: U.S. Patent Specification No. 4857583 (Japanese Patent Application Publication No. 1-87633) Patent Document 10: U.S. Patent Specification No. 5472987 (Japanese Patent Publication No. 2599237) Patent Document 11: U.S. Patent Specification No. 5696192 (Japanese Patent Application Publication No. 9-202829) Patent Document 12: US Patent Specification No. 6593436 Patent Document 13: International Publication No. 2005/103117 Patent Document 14: US Patent Specification No. 8008407 (Japanese Patent Publication No. 5101598) Patent Document 15: International Publication No. 2018/074257 (US20200048427A1)

As explained above, the average molecular weight of the (AB)n-type polyether-modified silicone copolymer can be designed, and the surface activity and the effect on the urethane foam system can be changed depending on the EO/PO ratio of the polyether portion, size, weight percent of the silicone portion, etc. Because affinity, etc. can be controlled, it is expected to be effective as a foam control or foam stabilizing surfactant in various polyurethane foam formulations. However, the known technology has problems such as manufacturing problems directly related to industrial production costs as described above, performance and quality problems, and insufficient market penetration despite its potential value due to these problems.

A composition containing (AB)n-type polyether-modified silicone and a specific glycol ether compound, a foam stabilizer, etc., previously proposed by the present inventors in Patent Document 6, was capable of solving the above problems to some extent, but the present inventors used the composition In obtaining the glycol ether compound, a new problem was discovered in that the quality of the glycol ether compound greatly influences the quality during its manufacture. In other words, if a glycol ether compound that is inexpensive but has a high acid value is used, the entire composition becomes low in viscosity during the hydrosilylation reaction, resulting in a decrease in foam stabilizing properties, or its transparency (light transmittance) is impaired and the expected performance as a foam stabilizing agent is not sufficiently achieved. There are cases where it becomes impossible to achieve.

In addition, the inventors have discovered new problems and solutions in the present invention that are not described in these patent documents. Recently, in the production of microcellular foam, which is the main use of (AB)n-type polyether-modified silicone, foam retention ability has become an important required characteristic for the foam stabilizer. Specifically, it is possible to reduce the amount of foaming agent added (cost reduction) and even when low-density foam is designed by increasing the amount of foaming agent or inflow gas, it is easy to obtain a foam with acceptable physical properties (energy reduction due to weight reduction) Due to the realization of savings, there is a strong demand for foam stabilizers for microcellular foams with strong foam holding power.

Here, the conventional method for improving foam retention is to design a foam stabilizer formulation to obtain n-number high molecular weight and high-viscosity products, that is, by setting the C=C/SiH molar ratio of the raw polyether and polysiloxane to a value close to 1.0. This causes it to react. However, with this method, it is known that the viscosity of the resulting foam stabilizer is greatly affected by slight measurement errors in raw materials, quality fluctuations for each production lot, or slight differences in manufacturing conditions, and the frequency of non-standard products being manufactured is also high. There is a big problem. Additionally, products with high viscosity have poor productivity and handleability, which inevitably leads to additional cost increases.

The technology of Patent Document 6 provided some improvement in this complex and complex problem, but left room for further improvement in terms of industrial simplicity and improvement in production efficiency. In particular, since foaming agents are required to be supplied industrially in large quantities and stably at low prices, foaming agent compositions obtained using conventional techniques that require advanced production management remain unsolved issues in distributing them to the market.

In consideration of the above market demands for silicone foam stabilizers for polyurethane foam and the spread of high-performance silicone foam stabilizers in the market, we have developed a stable and easy-to-use product that is low-cost, difficult to be influenced by errors in the weight of raw materials or lot (acid value, etc.), and is stable and easy to use. It is manufacturable, has excellent cost-in-use and supplyability, and has sufficient performance when used as a foam stabilizer for polyurethane foam, especially foaming properties and foam enhancement properties in the foam system. There is a strong demand for the development of a foam control agent using (AB)n-type polyether-modified silicone with cell control properties and cell stability, a manufacturing process thereof, and a prescription using the same.

In order to solve the above problems, the present inventors have intensively studied and found a method for producing a composition containing a polyether-polysiloxane block copolymer (A') of a specific structure having the following steps 1 to 3 (hereinafter referred to as “this method”) It was found that the above problem could be solved by the "manufacturing method" or "the manufacturing method of the present invention"), and the present invention was achieved.

Process 1: At least

(a1) polyether containing alkenyl groups at both ends, and

(N+S) Sodium salt solution containing the following component (N) and component (S)

(N) sodium salt of a monovalent carboxylic acid having a carbon atom number in the range of 2 to 18,

(S) one or more solvents selected from (S1) water and (S2) monohydric saturated alcohols having 1 to 4 carbon atoms

A process of mixing raw materials containing;

Process 2:

A step of removing the solvent (S) of step 1 from the system by heating and/or reduced pressure;

Step 3: Hydrosilylation of the components (a1) and (a2) organopolysiloxane containing SiH groups at both ends in the presence of the components (N) and (B') specific glycol ether compounds and a hydrosilylation reaction catalyst. Process (however, when the total amount of component (a1), component (a2) and component (B') is 100 parts by weight, the amount of component (B') used is in the range of 40 to 80 parts by weight, and component (B') The content of sodium cations (Na ⁺ ) in component (N) is in the range of 3.8 to 43 wt.ppm relative to the amount used.)

In this manufacturing method, the above steps 1 to 3 can be performed in one reaction vessel, and it is also preferable. Additionally, step 1 may be a mixing step of raw material components including other raw material components, as long as the component (a1) and component (N+S) are mixed. However, in step 1, it is extremely desirable that the component (a2) and the hydrosilylation reaction catalyst do not coexist in the raw material system.

This manufacturing method includes a process of filtering the composition after the hydrosilylation reaction; After the hydrosilylation reaction, a polyether compound that is compatible with the components (A') and (B') and is selected from specific components (C1) to (C3) is added and mixed and homogenized; and a step of adding an antioxidant at an arbitrary timing.

In addition, the above problem is (A'') a polyether-polysiloxane block copolymer having a specific structure, (B') a specific glycol ether compound, and (N) a monovalent carboxylic acid sodium having a carbon atom number in the range of 2 to 18. Containing a salt, the mass ratio of component (A''):component (B') is in the range of 20:80 to 60:40, and for the sum of component (A'') and component (B'), A foam-enhancing composition containing sodium cations (Na ⁺ ) in the component (N) in the range of 0.6 to 6.7 wt.ppm (hereinafter sometimes referred to as “this foam-enhancing composition”) and the above-mentioned problems by using the same. It was found that it was possible to solve the problem, and the present invention was arrived at.

In addition, the above problem is solved by a surfactant, a foam stabilizer for polyurethane foam, or a premix solution for polyurethane foam (hereinafter referred to as “surfactant, etc.”) containing the composition obtained by the present invention. Likewise, the above problems are solved by a method for producing surfactants including the present production method, a polyurethane foam forming composition containing the present composition or the present composition obtained by the above production method, and a polyurethane foam using these as raw materials. do.

By the manufacturing method of the present invention, the influence due to the quality and lot variation of the raw materials is suppressed, and although it is low-cost, it is difficult to be influenced by the measurement error of the raw materials or the lot (acid value, etc.), so it can be manufactured stably and easily, and the cost is low. A production method comprising an improved hydrosilylation reaction process of an (AB)n-type polyether-modified silicone composition that has excellent phosphorus use and supply properties and sufficient performance in use as a foam stabilizer for polyurethane foam, and the production method The composition obtained can be used as an anti-foaming agent.

In particular, by the production method of the present invention, even when a low-priced glycol ether compound is used as a raw material, (AB)n has a very low acid value and has the same quality and performance as a foaming agent as when a high-priced glycol ether compound is used as a raw material. Since it is possible to provide a polyether-modified silicone composition, it becomes possible to manufacture high-performance (AB)n-type polyether-modified silicone-based surfactants (especially foam stabilizers) in a stable and large quantity at low cost. It is expected that it will be possible to widely distribute these in the market.

In addition, the foam-enhancing composition according to the present invention can be manufactured stably and easily, has excellent cost-in-use and supplyability, and has sufficient performance when used as a foam stabilizer for polyurethane foam, especially foamability in polyurethane foam systems. , it is possible to provide a (AB)n-type polyether-modified silicone composition having cell enhancement, cell control, and cell stability.

More specifically, the present invention is particularly excellent in terms of fine cell formation, foam retention, foam force, and foam volume in various fields such as high-density microcellular foam by mechanical foaming method and other hard foams and soft foams. In addition, it is possible to provide a polyether-polysiloxane block copolymer composition that has excellent premix homogeneity and stability, and also has excellent compatibility with various components in the foam-forming emulsion composition. Additionally, a foam stabilizer for polyurethane foam consisting of the composition can be provided.

In addition, the composition according to the present invention is prepared by using the component (A''), component (B'), and a specific amount of component (N), so that the (AB)n-type polyether has low viscosity or does not have a very large molecular weight. Even if it is a modified silicone foam stabilizer, it has specifically enhanced surface activity and foam retention ability, so it can secure sufficient performance for practical purposes even without setting the C=C/SiH molar ratio close to 1.0 during manufacturing. It has the advantage of making production management easier.

Figure 1 is a diagram showing the relationship between the amount of sodium ion (Na) added to BDPG [ppm] and the viscosity change rate of the polyether-polysiloxane block copolymer composition, and its target level.
Figure 2 is a diagram showing the relationship between the sodium ion (Na) content [ppm] in the composition and the foam holding power [cm] of the polyether-polysiloxane block copolymer composition, and its target level.

Hereinafter, a method for producing a composition containing the polyether-polysiloxane block copolymer of the present invention using an improved hydrosilylation reaction process will be described in detail. First, each raw material used in manufacturing the above composition will be explained, including its relationship with the manufacturing process.

[Raw ingredient (a1)]

Component (a1) has the following general formula (1):

[Tuesday 1]

(In the formula, x is a number from 2 to 4, y represents a number in which the molecular weight of the _polyether portion represented by ( _C Represents a monovalent hydrocarbon group having 2 to 8 carbon atoms having a C group, and the polyether portion contains at least 1 oxypropylene group)

It is a polyether containing alkenyl groups at both ends, and the polyether-polysiloxane block copolymer (A') is given by hydrosilylation reaction with component (a2) described later.

Here, the group Y can be selected from vinyl group, allyl group, methallyl group, isoprenyl group, hexenyl group, octenyl group, etc., but is particularly preferably allyl group and/or methallyl group. _y is preferably a number such that the molecular weight _of the polyether portion _represented by _{( C} It is preferable that the mass ratio is within the range of 30 to 80% on average.

Component (a1) is generally produced by subjecting a polyether having a hydroxyl group at the terminal and a strong alkali alcoholate to a nucleophilic substitution reaction with a halogenated alkenyl, and then removing low-boiling substances, by-produced salts, etc. In this reaction, the blocking rate of the hydroxyl group is often not complete, and the group Y usually contains a small amount of hydroxyl group as an impurity. The blockage ratio is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 98 mol% or more.

The moisture content contained in component (a1) is preferably 0.5 wt.% or less, more preferably 0.2 wt.% or less, and particularly preferably 0.1 wt.% or less. Since component (a1) is prone to moisture absorption, depending on the circumstances, dehydration treatment may be performed in the reactor before starting the hydrosilylation reaction.

Additionally, since component (a1) is prone to oxidative degradation, approximately 100 to 1000 ppm of an antioxidant may be added after completion of the synthesis reaction of component (a1) and dissolved in the raw materials. One example of a suitable antioxidant is vitamin E.

[Ingredients (N+S)]

Component (N+S) is one of the characteristic components of the manufacturing method of the present invention, and is a buffer system that has the function of neutralizing trace amounts of acid derived from the raw material component (B') and other raw materials, which will be described later. A composition containing copolymer (A') or (A') and (B') as main components, suppressing side reactions during production of the polyether-polysiloxane block copolymer (A') and achieving desired design and quality/ It can make it possible to obtain a purifying agent stably and efficiently. On the other hand, in the buffer system, the amount of component (B') used is within the range of 40 to 80 parts by weight based on a total of 100 parts by weight of component (a1), component (a2) described later, and component (B'), and then used as described later. The amount of component (N) needs to be within the range of 3.8 to 43 wt.ppm in terms of sodium ion, relative to the actual amount of (B') used. Even if the above conditions are not satisfied or other buffering agents are used, the purpose of the present invention may not be sufficiently achieved.

In addition, in the production method according to the present invention, it is particularly preferable that the sodium content in the composition is within the range of 0.6 to 6.7 wt.ppm with respect to the entire composition. This is because, if it is within the range, in addition to manufacturing advantages, the foam enhancing effect described later can be realized.

More specifically, the component (N+S) is one type selected from (N) monohydric sodium carboxylate having 2 to 18 carbon atoms, (S1) water, and (S2) monohydric saturated alcohol having 1 to 4 carbon atoms. It is a sodium salt solution containing the above solvent.

Component (N) is a sodium salt of a monovalent carboxylic acid having 2 to 18 carbon atoms, which is a buffer component, and is preferably at least one type selected from sodium salts of a monovalent carboxylic acid having 2 to 8 carbon atoms, and is a sodium salt of a monovalent carboxylic acid having 2 to 4 carbon atoms. One or more types selected from the following are particularly preferable. Examples of such include sodium acetate, sodium propionate, sodium butyrate, etc., with sodium acetate being the most preferable.

Component (S) is a solvent for component (N) and is one or more liquid compounds selected from (S1) water and (S2) monohydric saturated alcohols having 1 to 4 carbon atoms. By using component (S), the sodium salt containing the counteranion can be added and dispersed uniformly and easily in the system. In addition, component (S) preferably has excellent solubility of component (N), compatibility with other components, and safety, and may be a mixture of two or more types selected from the above components (S1) and (S2).

(S1) is water, and it is preferable to use water with few impurities, such as ion-exchanged water, pure water, ultrapure water, purified water, distilled water, or tap water.

Specific examples of (S2) include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, and isobutyl alcohol. From the viewpoint of salt dissolving power, methanol or ethanol is preferable, and from the viewpoint of safety, ethanol or isopropyl alcohol is preferable.

The concentration of (N) carboxylic acid sodium salt in the sodium salt solution, which is the raw material component (N+S), varies depending on the solubility of the salt used in the solvent used, but in practical terms, it is 0.5 to 20 wt.%, preferably 1 to 10 wt. It is good to be within the range of .%. (S1) Water is often a good solvent for sodium salts of monovalent carboxylic acids having 2 to 18 carbon atoms, and depending on the type of salt, it may be dissolved at a concentration of 30 wt.% or higher. It is okay to use such a high-concentration solution as is, but it is necessary to keep in mind that the impact of measurement error is large because the number of additions as a solution is small. Also, whether it was possible to quantitatively inject the raw material into the raw material system without loss: Caution and measures are also needed to ensure that the material does not stay in the middle of the input line. Additionally, in preparing the raw material components (N+S), a high-concentration aqueous solution can be prepared first, and then (S2) can be diluted by adding an appropriate amount of saturated monohydric alcohol having 1 to 4 carbon atoms.

The sodium salt solution containing component (S) is mixed with a raw material system containing at least component (a1). As a result, compared to the case where component (N) is mixed as a solid particle into the raw material system, a uniform and fine dispersion state is achieved, and acid impurities originating from the raw material system (particularly, raw material component (B') described later) are effectively removed. It can be neutralized. In addition, it is advantageous in terms of the appearance (transparency) of the product system after completion of the hydrosilylation reaction, and there is an advantage in that the burden of performing the filtration purification process afterwards is lightened.

In the present invention, component (S) is prepared by a known means involving heating and/or pressure reduction, such as stripping, before the start of the hydrosilylation reaction, for the purpose of preventing side reactions in the process after adding component (N) to the system. It is removed from the public by . The mixture after removing component (S) contains at least the raw material component (N) and component (a1), and component (N) is uniformly and finely dispersed in the mixture.

[Raw ingredient (a2)]

Component (a2) is an organopolysiloxane containing SiH groups at both ends represented by general formula (2).

General formula (2):

[Tuesday 2]

(wherein R each independently represents a monovalent hydrocarbon group having 1 to 9 carbon atoms without an aliphatic unsaturated bond, and a represents a number from 1 to 200), and in the hydrosilylation reaction with the component (a1) The polyether-polysiloxane block copolymer (A') is provided by this method.

Here, particularly preferred R is a methyl group. In addition, from the viewpoint of usefulness and handleability of the foam stabilizer produced, in the above general formula (5), a is preferably a number in the range of 10 to 45.

For component (a2), organodisiloxane containing SiH groups at both ends and low-molecular-weight cyclic diorganosiloxane are usually added at a desired molar ratio, polymerization is carried out in the presence of an acid catalyst, and the catalyst is neutralized after reaching an equilibrium state, It is manufactured by removing neutralizing salts, etc. Due to the nature of the equilibrium reaction, it is common that 10 to 15 wt.% of low-molecular-weight cyclic diorganosiloxane, in addition to the target organopolysiloxane containing SiH groups at both ends, remains in the production system.

Here, when the polyether-polysiloxane block copolymer composition according to the present invention is used as a foam stabilizer for low VOC/emission type polyurethane foam, it is preferable that the composition substantially does not contain low molecular weight siloxane with a silicon atom number of 20 or less.

Meanwhile, in the method for producing the present composition, production efficiency is greatly improved if a stripping process is substantially eliminated after synthesis of the copolymer (i.e., after hydrosilylation reaction). In particular, it is preferable to avoid the stripping process after synthesizing the copolymer because it is likely to cause violent foaming accompanying pressure reduction. Therefore, it is desirable to remove low molecular weight siloxane, especially low molecular weight cyclic siloxane, from component (a2) in advance. There are numerous methods for removing low molecular weight siloxanes from component (a2). For example, a method of treating the equilibrium mixture of organopolysiloxane containing SiH groups at high temperature and high vacuum while blowing a small amount of inert gas such as argon gas or nitrogen gas into the equilibrium mixture of organopolysiloxane containing SiH groups, thinning the equilibrium mixture of organopolysiloxane containing SiH groups, e.g. For example, a method of stripping under reduced pressure of 0.5 mm or less and heating conditions of 50 to 130°C, an equilibrium mixture of SiH group-containing organopolysiloxane with an organic solvent that dissolves low molecular weight siloxane and does not dissolve high molecular weight siloxane, such as methanol. There is a method to extract and remove low molecular weight siloxane by adding organic solvents such as ethanol and acetone.

Specifically, component (a2) preferably has a total content of low-molecular-weight cyclic siloxanes having a silicon atom number of 6 or less of 3000 ppm (by weight) or less, and particularly preferably 300 ppm (weight) or less. As such low molecular weight cyclic siloxane, for example, cyclic dimethylsiloxane represented by the formula [(CH3)2SiO]n (where n is an integer of 3 to 10) is representative. In addition, the content of low-molecular-weight siloxane in component (a2) can be measured, for example, by diluting component (a2) with an organic solvent and introducing the diluted solution into a gas chromatographic analysis device for analysis.

[Component (B')]

Component (B') has a terminal hydrogen substituted by a hydrocarbon group having 1 to 8 carbon atoms, and also has a secondary alcoholic hydroxyl group at the other terminal, and a repeating number of an oxyalkylene unit having 2 to 4 carbon atoms in the range of 1 to 3. It is one or two or more types of glycol ether compounds characterized by being water and containing no heteroatoms other than oxygen. In the production method according to the present invention, component (B') is introduced into the composition as a solvent in the synthesis reaction of component (A'), and is used in combination with other components in the composition, that is, in the handling properties of the foam stabilizer or in the polyurethane foam formulation. It has the function of improving compatibility with other products.

Component (B') is preferably a monool organic compound having a boiling point that can be purified by distillation or distillation. Examples of such compounds include propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monobutyl. Ether, Propylene Glycol Monomethyl Ether, Dipropylene Glycol Monomethyl Ether, Tripropylene Glycol Monomethyl Ether, Propylene Glycol Monopropyl Ether, Dipropylene Glycol Monopropyl Ether, Tripropylene Glycol Monopropyl Ether, Propylene Glycol Monoethyl Ether, Dipropylene One or two or more types of glycol ethers selected from glycol monoethyl ether and tripropylene glycol monoethyl ether can be mentioned. Particularly preferred are one or two or more glycol ethers selected from dipropylene glycol monobutyl ether and tripropylene glycol monobutyl ether.

In the production method according to the present invention, when a single glycol ether is used, its purity is preferably at least 90 wt.%. Preferably, the purity is 95 wt.% or more, and particularly preferably 98.5 wt.% or more. Even when multiple types of glycol ethers are used together as raw materials iv), the purity of each glycol ether is preferably high as described above.

Additionally, as mentioned above, component (B') may contain trace amounts of acidic substances due to the manufacturer or storage conditions. The content of the acidic substance in component (B') is preferably 0.02 wt.% or less, more preferably 0.01 wt.% or less, and especially preferably 0.001 wt.% or less.

The moisture content contained in component (B') is preferably 0.5 wt.% or less, more preferably 0.2 wt.% or less, and particularly preferably 0.1 wt.% or less. Since component (B') is prone to moisture absorption, depending on the circumstances, dehydration treatment may be performed in the reactor before starting the hydrosilylation reaction.

In the composition obtained by the production method according to the present invention, the mass ratio of component (A'):component (B') is in the range of 20:80 to 60:40. Therefore, the amount of component (B') used in the composition is 40 to 80 parts by weight based on a total of 100 parts by weight of the raw materials (a1), (a2), and component (B'). It is important in terms of performance, quality, convenience in use, and handling.

[Raw ingredient: hydrosilylation reaction catalyst]

In the production method according to the present invention, component (a1) and component (a2) described above undergo a hydrosilylation reaction in the presence of an effective amount of a hydrosilylation reaction catalyst to form component (A'). Here, the hydrosilylation reaction catalyst is not limited to a specific catalyst as long as it can promote the hydrosilylation reaction, and may be appropriately selected from known hydrosilylation reaction catalysts and used in the present invention. Specific examples of hydrosilylation reaction catalysts include fine particulate platinum adsorbed on silica fine powder or carbon powder carrier, chloroplatinic acid, alcohol-modified chloroplatinic acid, olefin complex of chloroplatinic acid, coordination compound of chloroplatinic acid and vinylsiloxane, platinum such as platinum black. A hydrosilylation reaction catalyst containing a can be mentioned.

In the production method according to the present invention, a particularly suitable hydrosilylation reaction catalyst is a neutral platinum complex catalyst, and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex is particularly preferred. On the other hand, when using an acidic hydrosilylation reaction catalyst such as chloroplatinic acid or alcohol-modified chloroplatinic acid, the use or increase of the (N) specific monovalent carboxylic acid sodium salt or other buffering agent constituting the buffering system is required. There are cases.

The amount of the hydrosilylation reaction catalyst used is an effective amount and is not particularly limited, but when the total mass of component (a1) and component (a2) is 100% by mass, the metal atom (particularly the platinum group metal atom) in the hydrosilylation reaction catalyst The amount is 0.1 to 200 ppm in mass units, and the amount is preferably in the range of 1 to 50 ppm. This means that if the content of the hydrosilylation reaction catalyst is less than the above lower limit, the progress of the copolymerization reaction by the hydrosilylation reaction may become insufficient, and if it exceeds the above upper limit, it is uneconomical and affects the transparency, such as coloring, of the resulting composition. This is because there are cases where it can have a negative impact.

[Raw Ingredients: Antioxidants]

The polyether-polysiloxane block copolymer composition according to the present invention may be gradually oxidized and deteriorated by oxygen in the air. To prevent this, oxidation stability can be improved by adding antioxidants such as phenol-based, hydroquinone-based, benzoquinone-based, aromatic amine-based or vitamins. As such antioxidants, for example, BHT (2,6-di-t-butyl-p-cresol), vitamin E, etc. can be used.

The antioxidant is preferably contained in a range of 1 to 1000 wt.ppm, more preferably 50 to 500 wt.ppm, based on 100 parts by mass of the total of component (A'), component (B'), and optionally component (C). The range is ppm.

In the production method of the present invention, the timing of adding the antioxidant to the production raw material system is arbitrary, and may be added to the raw material or the composition after synthesis at any time including before and after the hydrosilylation reaction. In particular, the above quantitative range is It is preferably added together with the above component (a1).

[Raw ingredients: other buffering agents]

In the production method of the present invention, the buffer system is a carboxylic acid sodium salt solution of the above components (N+S), but optionally, additionally

(K) a potassium salt consisting only of carbon, hydrogen, and oxygen, having a carbon atom number within the range of 1 to 8, and having a monovalent counteranion that does not contain a benzene ring structure;

And other buffering agents selected from alkali metal salts or alkaline earth metal salts may be added.

As an example, other potassium salts that serve as buffering agents include potassium carbonate, potassium benzoate, potassium lactate, potassium laurate, potassium oleate, potassium bicarbonate, potassium acetate, potassium propionate, potassium butyrate, potassium isobutyrate, and 2-ethyl. Potassium hexanoate, etc. may be mentioned, but it is not limited to these.

In the case of addition of a buffering agent, together with component (N) or separately from component (N), the buffering agent is dissolved or dispersed in water and/or monohydric saturated alcohol having 1 to 4 carbon atoms as the component (S). It is preferred to incorporate this composition in the form of a solution. In addition, the buffering agent may be used as a solid as long as it does not impair the technical effect of the invention.

[Raw ingredients: Other neutralizers]

In the production method of the present invention, together with the sodium salt solution as the component (N+S), as a neutralizing agent,

(M) The following general formula:

[Tuesday 3]

(Wherein, R' represents a monovalent hydrocarbon group having 1 to 18 carbon atoms, R" represents a methyl group or an ethyl group, p represents a number from 0 to 20, q represents a number from 1 to 20, (poly) The bonding form of the oxyethylene moiety and the other (poly)oxyalkylene moiety may be random or block.)

A (poly)oxyalkylene tertiary amine compound represented by may be added in an appropriate amount.

These (poly)oxyalkylene tertiary amine compounds are specifically, R'N[(CH ₂ CH ₂ O) ₄ {CH ₂ CH(CH ₃ )O} ₄ H] ₂ (R'=coco alkyl group) Tertiary amine compounds expressed by average molecular formula, etc. can be mentioned.

These buffering agents (including solvents for dissolving or dispersing them) or neutralizing agents may be added to the production raw material system to the extent that they do not impair the technical effect in the production method according to the present invention. In addition to the sodium salt solution of the component (N+S), a hydrosilylation reaction is performed in the presence of the buffer or neutralizing agent, thereby neutralizing acidic substances in the production raw materials, such as component (B'). In addition to being able to further reduce the quality impact, depending on the type of additive, it may be possible to achieve a foam enhancing effect in the final composition.

[Component (A')]

The production method according to the present invention is an improved hydrosilylation reaction process of the above components (a1) and (a2), and gives a composition comprising the polyether-polysiloxane block copolymer (A') of a specific structure. Component (A') synthesized by this production method is a main agent such as a surfactant, and can be particularly used as a foam stabilizer for polyurethane foam.

Component (A') is one of the main components of the composition,

General formula (3):

[Tuesday 4]

It is a polyether-polysiloxane block copolymer that has a structural unit represented by in the molecule.

The terminal group of component (A') is not particularly limited as long as it satisfies the above structure, but when synthesized by the hydrosilylation reaction described later, the structure of the molecular chain terminal is

Z ¹ : Alkenyl group, hydroxyl group, alkoxy group or acetoxy group bonded to the polyether moiety; and

Z ² : Monovalent hydrocarbon group, hydroxyl group, alkoxy group, C1 to C8 hydrocarbon oxyalkylene oxy group or hydrogen bonded to a silicon atom and having no heteroatom

It is preferable that it is one or more types of functional groups selected from.

In the formula, R each independently represents a monovalent hydrocarbon group having 1 to 9 carbon atoms without an aliphatic unsaturated bond, and an alkyl group having 1 to 9 carbon atoms is exemplified. Industrially, a methyl group is particularly preferable. Y' is a divalent hydrocarbon group of 2 to 8 carbon atoms that is bonded to the polyoxyalkylene block by an oxygen atom and to an adjacent silicon atom by a carbon-silicon bond, and is preferably a divalent hydrocarbon group of 3 to 4 carbon atoms. And, it is especially preferable that it is an isobutylene group.

a is a number from 1 to 200, x is a number from 2 to 4, y represents a number in which the molecular weight of the polyether portion represented by (C _x H _2x O)y is in the range of 400 to 5000, and polyether The moiety contains at least 1 oxypropylene group, and n is a number of at least 2.

From the viewpoint of usefulness as a foaming agent and stability of the copolymer, it is preferable that one or both ends of the polyether-polysiloxane block copolymer as component (A') are blocked with a functional group containing a polyether moiety, in that case , the terminal group is represented by the above Z ¹ and is preferably an alkenyl group, a hydroxyl group, an alkoxy group, or an acetoxy group bonded to the polyether moiety, and particularly preferably a methallyl group. Additionally, when an organopolysiloxane containing SiH groups at both ends is used as the raw material for component (A'), some of the terminal SiH may react with the hydroxyl group of component (B'), which will be described later, and some of its terminal groups may be ( It may be a residue of a glycol ether derived from B').

On the other hand, it is preferable that the terminal group of component (A') does not contain a reactive functional group having a hetero atom, and in particular, it is preferable that it does not contain a ring-opening reactive reactive functional group such as an epoxy group or an amine group.

For component (A'), the average molecular weight of the copolymer can be designed by adjusting the molar ratio (reaction ratio) of the organopolysiloxane containing SiH groups at both ends and the polyether containing alkenyl groups at both ends, which are its raw materials. In addition, it is easy to control surface activity, affinity to the urethane foam system, etc. by controlling the EO% and size of the polyether portion and the introduction of hydroxyl or hydrophobic groups into the copolymer end portion. Therefore, the copolymer composition can exhibit excellent effects as a foam control or foam stabilizing surfactant in various types of polyurethane foam formulations.

[Especially suitable ingredient (A'') and specific foam enhancing effect, etc.]

From the viewpoint of usefulness and handling as a foam stabilizer, in the general formula (3), a is a number in the range of 10 to 45, and y is a number in which the molecular weight of the polyether (polyoxyalkylene) portion is in the range of 1500 to 5000. In addition, it is particularly preferable that the mass ratio of oxyethylene (C ₂ H ₄ O) units constituting the entire polyether portion is within the range of 30 to 80% on average. In the present invention, a polyether-polysiloxane block copolymer having a structure that satisfies the above conditions in general formula (3) is a particularly preferred form and is called component (A'').

In the above range, the hydrophilicity balance of the polyether-polysiloxane block copolymer is good, and a certain amount of oxypropylene units or oxybutylene units are inevitably included, so that polyol or isocyanate, which is the main component of the polyurethane foam forming composition, and static foam are added. The compatibility of the agent is improved, making it advantageous to increase convenience by improving the stability of the premix solution and to obtain a desirable foaming effect. The function as a surfactant or anti-foaming agent and the handling properties during or after synthesis are also improved.

In addition, in the composition comprising the polyether-polysiloxane block copolymer as component (A'') having a suitable structure, the component (B'), and component (N), when each component satisfies a defined quantitative relationship, In some cases, additional benefits such as foam enhancement may be obtained.

Specifically, the mass ratio of component (A'') and component (B') is component (A''): component (B') = 20 to 60: 80 to 40 (here, component (A'') and component (B') The total amount of (B') is set to 100), and the sodium salt of a monovalent carboxylic acid having 2 to 18 carbon atoms, which is component (N), is added to the total amount of component (A'') and component (B'). A composition containing 0.6 to 6.7 wt.ppm in terms of sodium has a specifically enhanced surface activity ability and foam retention ability, and is used as a surfactant, foam stabilizer for polyurethane foam, or a component of a premix solution for polyurethane foam. It is extremely useful.

[Production method of the present invention: steps 1 to 4]

The production method of the present invention essentially includes the following steps 1 to 3, and may additionally include an optional filtration step (step 4). In particular, from the viewpoint of industrial productivity and ensuring the quality of the resulting composition, in the production method of the present invention, it is particularly preferable to perform these steps 1 to 3 in one reaction vessel.

[Process 1: Mixing process of raw material ingredients]

Step 1 is a step of mixing raw material components containing at least a polyether containing alkenyl groups at both ends, which is the raw material component (a1), and a sodium salt solution, which is the component (N+S). By using component (S), the sodium salt of component (N) is uniformly and finely dispersed in the raw material component (a1), thereby preventing the It can effectively neutralize acid impurities. In addition, it is advantageous in terms of the appearance (transparency) of the product system after completion of the hydrosilylation reaction, and there is an advantage in that the burden of performing the filtration purification process afterwards is lightened. The mixing means in step 1 is not particularly limited as long as uniform mixing can be achieved, and mechanical mixing and stirring means using a mixer, stirring blade, etc. are convenient.

Here, step 1 may be a step of mixing one or more types selected from the component (a1), the component (N+S), and optionally other raw material components. For example, component (a1) and the antioxidant may be premixed and mixed together with the component (N+S), component (a1), component (a2), component (B'), component (N +S), additives such as antioxidants may be mixed in advance, and are not particularly limited in the production method of the present invention. However, it is preferable that component (a2) and the hydrosilylation reaction catalyst do not coexist in step 1. This is because, in steps 1 and 2, hydrosilylation reactions or side reactions in unexpected forms are likely to occur. Therefore, in step 1, it is preferable that component (a2) and the hydrosilylation reaction catalyst are added to the raw material system selectively, and in particular, it is preferable that the hydrosilylation reaction catalyst is not added to the raw material system in step 1. In addition, if the hydrosilylation reaction catalyst has excellent compatibility with component (a1) and does not cause deactivation upon contact with component (N+S), the catalyst may be used by dissolving it in component (a1). This is possible, but in other cases, scum may occur due to catalyst agglomeration and reaction efficiency may decrease, so caution is required.

In addition, depending on the raw material ingredients mixed in step 1, care must be taken that other raw material ingredients may need to be changed thereafter. For example, when only component (a1), component (N+S) and antioxidant are mixed in step 1, and removal of the solvent (S) described later is performed in step 2, the mixture after removing component (S) is Since it is a mixture consisting of component (a1), component (N), and antioxidant, other raw material component (a2), component (B'), and hydrosilylation reaction catalyst are further added to the mixture, and hydrosilylation in step 3 is performed. The reaction is carried out. On the other hand, if step 1 is a mixture containing all raw materials other than the hydrosilylation reaction catalyst, it is sufficient to add only the unadded hydrosilylation reaction catalyst to the mixture after removing component (S), and in step 3 A hydrosilylation reaction can be performed.

[Process 2: Removal process of solvent (S)]

Process 2 is a post-process of Process 1, and is a process in which component (S), which is a solvent, is removed from the system by known means involving heating and/or reduced pressure, such as stripping, for the purpose of preventing side reactions. If component (S) is not removed from the raw material in step 2, it may not be possible to solve the technical problem of preventing side reactions in the hydrosilylation reaction process when inexpensive and low-purity raw material component (B') is used. . In addition, the mixture after removing component (S) contains at least the raw material component (N) and component (a1), and component (N) takes the form of being uniformly and finely dispersed in the mixture.

[Process 3: Hydrosilylation reaction process]

Step 3 is hydrosilylation in the presence of a mixture containing the raw material component (N) and component (a1) obtained in Step 2, a solution containing the component (a2), the component (B'), and a hydrosilylation reaction catalyst. Reaction step (however, when the total amount of component (a1), component (a2) and component (B') is 100 parts by weight, the amount of component (B') used is in the range of 40 to 80 parts by weight, and component (B It is characterized by having a content of sodium cations (Na ⁺ ) in the component (N) in an amount ranging from 3.8 to 43 wt.ppm relative to the amount used. Here, the amount of component (N) used is particularly such that the sodium cation (Na ⁺ ) content is within the range of 0.6 to 6.7 wt.ppm relative to the total amount of component (a1), component (a2), and component (B'). desirable. By this hydrosilylation reaction process, (A') the general formula (3):

[Tuesday 5]

A polyether-polysiloxane block copolymer having a structural unit represented by in the molecule is synthesized. In the present invention, it is particularly preferable to obtain a polyether-polysiloxane block copolymer (A'') having a structure that satisfies the above conditions, particularly preferably in general formula (3).

In the hydrosilylation reaction process according to the present invention, the amount of the terminal alkenyl group (R-Vi) in component (a1) is equivalent to or slightly in excess with respect to the silicon atom bonded hydrogen atom (Si-H) in component (a2). It is preferable that the amount is, and more specifically, it is preferable that the substance amount ratio (molar ratio) expressed as [R-Vi]/[Si-H] is 1.0 to 1.5, and it is especially preferable that it is in the range of 1.1 to 1.2. .

As described in Patent Document 6 (International Publication No. 2016/166979), there is generally a correlation between the types of silicones and foaming resins containing the polyether portion, which is a foam stabilizer, and low molecular weight foams are suitable, while high molecular weight foams are suitable. If you list the appropriate forms in order,

High elasticity foam < hard foam < soft foam < microcellular foam.

In addition, since the structure of the polyether part greatly affects the size of the foam, etc., in cases where the cell size is reduced to lower breathability, a polyether structure with a high EO content should be selected, or in cases where the foam is stabilized and maintained. In order to select a polyether with a large molecular weight, expand the process range, or use multiple polyethers with different molecular weights and structures as raw materials to ensure suitability for a wide range of uses and prescriptions, the molecular weight distribution of the polyether portion is determined. There are methods such as widening, and these methods are applicable to the polyether-polysiloxane block copolymer composition and its production method according to the present invention. In addition, since polyol, which is one of the main raw materials of polyurethane, has a PPG structural moiety, it is often desirable to further contain a PO (propyleneoxy) chain in the polyether portion of the polyether-modified silicone from the viewpoint of compatibility in foam formulations. .

The requirement for a foam stabilizer varies depending on the type of polyurethane foam into which the (AB)n-type polyether-modified silicone composition according to the present invention is blended, but for example, it contains SiH groups at both ends represented by the above general formula (2). By appropriately adjusting the chain length of the organopolysiloxane (a2), the type of polyether (a1) containing alkenyl groups at both ends represented by the general formula (1), their reaction rate and mass ratio, etc., or the EO/ Since the surface activity ability and affinity to the urethane foam system can be controlled by PO% and molecular weight, a suitable foam stabilizer can be freely designed according to desire.

The hydrosilylation reaction conditions according to the present invention can be selected arbitrarily, but a small amount of antioxidant such as tocopherol (vitamin E) is added and heated at room temperature to 200°C, preferably 50 to 100°C, in an inert gas atmosphere such as nitrogen. It can be obtained by stirring. In addition, antioxidants may be added after completion of the hydrosilylation reaction. The reaction time can be selected depending on the reaction scale, amount of catalyst used, and reaction temperature, and is generally in the range of minutes to several hours. In addition, the reaction may be performed under reduced pressure for the purpose of quality improvement, etc., and for example, the reaction conditions proposed in Patent Document 4 (Japanese Patent Application Publication No. 11-116670) can be applied without particular restrictions. .

The end point of the hydrosilylation reaction can be confirmed by the disappearance of Si-H bond absorption by infrared spectroscopy (IR) or the disappearance of hydrogen gas generation by the following alkali decomposition gas generation method. In addition, the amount of hydrogen gas generated can be determined by analyzing the silicon atom-bonded hydrogen atoms (Si-H) in the organopolysiloxane containing SiH groups at both ends, which is a reaction raw material, by the same method. Below is his outline.

<Alkaline decomposition gas generation method: A solution in which a sample is dissolved in toluene or IPA and a 28.5 mass% caustic potassium ethanol/water mixed solution are reacted at room temperature, and the generated hydrogen gas is collected in a collection tube and its volume is measured>

In the method for producing this composition, it is preferable not to include a stripping process after the process of synthesizing the polyether-polysiloxane block copolymer (A') by hydrosilylation reaction. This is to avoid foaming during the manufacturing process after the synthesis of component (A'). In addition, the composition containing the above component (A') and component (B') as main components preferably has a viscosity in the range of 100 to 60,000 mm2/s at 25°C in terms of convenience in use, handling, etc. .

[Process 4: Filtration process]

In the method for producing the present composition, it is preferable to optionally further include a filtration step of the obtained composition after the hydrosilylation reaction. Here, the means such as filters and filter media used for filtration can be appropriately selected depending on the production scale and the type or degree of foreign substances, but can reduce waste, ensure worker safety, ensure work efficiency, and ensure quality and performance in the use of this composition as a foaming agent. From this point of view, the use of zeta potential type adsorption filtration filters, bag filters, cartridge filters, etc. is suitable. In addition, step 4 can be performed at any timing before or after the addition of component (C), which will be described later, and can be performed twice or more depending on the desired light transmittance, etc.

The filtration process is not particularly limited, but the composition after the hydrosilylation reaction may be filtered so that the light transmittance (580 nm) is 90% or more, more preferably 95% or more.

[Addition of component (C)]

In the method for producing the present composition, the following component (C) is further added to the composition containing the above component (A') and component (B') as main components so that the content of component (A') is 1% by mass or more. It can also be added to mix and homogenize.

Component (C) is a polyether compound that is compatible with component (A'), component (B'), and component (N1) after synthesis, and is selected from the following components (C1) to (C3), and the entire composition is mixed and homogenized. By doing so, there is an advantage in that the viscosity, etc. of the composition according to the present invention can be adjusted without adversely affecting the function of the present composition as a foaming agent or surfactant, thereby improving convenience in use and handling workability (handling). In addition, component (C) can be used for the purpose of adjusting the hydroxyl value of the polyurethane foam forming composition containing the present composition, that is, controlling various physical properties such as crosslinking density and strength of the polyurethane foam, and is preferred. In addition, the timing of adding component (C) to the system can be arbitrarily selected.

(C1) Polyether monool represented by the following general formula (4).

General formula (4):

[Tuesday 6]

(In the formula, R represents a monovalent hydrocarbon group having 1 to 9 carbon atoms without an aliphatic unsaturated bond, R" represents a methyl group or an ethyl group, k is 0≤k≤20, and l is 4≤l≤50. is satisfied, and the wt.% of the oxyethylene portion of the polyether portion is 60 or less),

A preferred specific example of component (C1) is polypropylene glycol n-butyl ether with k=0, R=nC ₄ H ₉ , R"=CH ₃ , which has the advantages of being easy to handle and readily available at low cost. In particular, the range of 4≤l≤33 is preferable because it has excellent compatibility with the composition. In addition, when pursuing low VOC or reducing the concentration of hydroxyl groups derived from (C1), 10≤l≤ It is preferable that it is in the range of 33.

(C2) A polyether diol represented by the following general formula (5).

General formula (5):

[Tuesday 7]

(In the formula, R" has the same meaning as above, k' satisfies the conditions of 0≤k'≤10, l' satisfies the conditions of 4≤l'≤70, and also represents the wt.% of the oxyethylene portion of the polyether portion. is less than 30)

Preferred specific examples of component (C2) include polypropylene glycol with k'=0 and R"=CH ₃ , which has the advantage of being easy to handle and readily available at a low price. In particular, 4≤l'≤34 The range is preferred because it has excellent compatibility with the composition.

(C3) The wt.% of the oxyethylene portion of the polyether portion is 20 or less, the average molecular weight is within the range of 500 to 4500, and is suitable for addition polymerization of alkylene oxide having 2 to 4 carbon atoms to glycerin and/or trimethylolpropane. polyether triol obtained by.

Preferred specific examples of component (C3) include polyether triol obtained by addition polymerization of propylene oxide to glycerin, and those with an average molecular weight of about 1500 to 3500 are easy to handle and are particularly compatible with the composition. It is desirable because it is excellent.

Component (C) can be contained in such a range that the content of component (A') is 1% by mass or more with respect to the composition.

The timing of adding component (C) is preferably after the hydrosilylation reaction, and at this time, the viscosity of the entire composition containing component (C) at 25°C is in the range of 100 to 35,000 mm ² /s. If desired, the contents of component (C), component (A'), and component (B') may be adjusted to satisfy the viscosity range or according to the required physical properties of the polyurethane foam, thereby mixing and homogenizing them. In addition, as already explained, the technical intention of adding component (C) is not limited to adjustment of viscosity, etc.

The mass ratio of the component (A') and the component (B') is within the range of 20/80 to 60/40, and the amount of the carboxylic acid sodium salt relative to the actual amount of component (B') used is 3.8 to 3.8 in sodium terms. The composition further containing the component (C) within the range of 43 wt.ppm is useful as a foam control agent or surfactant, especially as a foam control agent for polyurethane foam or as a premix solution for polyurethane foam.

In particular, component (A') after synthesis satisfies the structural characteristics of component (A''), and the mass ratio of component (A'') and component (B') is 20/80 to 60/ 40, and contains a sodium salt of a monovalent carboxylic acid having 2 to 18 carbon atoms in the range of 0.6 to 6.7 wt.ppm in terms of sodium relative to the total amount of component (A'') and component (B'). , Compositions to which component (C) is added in a range of 1 to 20% by mass of component (A'') are particularly useful for the above applications, and not only are they superior in terms of production, but also have unique properties such as foam enhancement effects as a composition. Technical effects can be expected.

[Other optional ingredients]

The composition obtained by the production method of the present invention is preferably used mainly as a surfactant, and within the range that does not impair its technical characteristics, it can be used as other organic modified silicones such as polyether modified silicones, straight silicones, organic surfactants, etc. It may also include . In this case, it is preferable that their content does not exceed the same amount relative to the mass of the component (A') in the entire composition. In addition, this composition can also be suitably used for applications such as surfactants, especially as foam stabilizers for polyurethane foam.

To this composition, at least a part of the components that can be used in the polyurethane foam-forming composition described later can be added in advance as other optional components to the extent that the technical effect of the present invention is not impaired.

In the method for producing this composition, other optional components already described, the component (B'), and component (C) may be added and mixed and homogenized. In addition, in the method for producing the present composition, at least a part of the components that can be used in the polyurethane foam-forming composition described later as other optional components are added to the present composition, mixed and homogenized, to the extent that the technical effect of the present invention is not impaired. It may be possible. This has the advantage of being able to prepare a homogeneous premix solution for polyurethane foam containing a foam stabilizer component and desired components.

Organic solvents may be used in this composition, but in the production method of the present invention, the use and mixing of aromatic hydrocarbon solvents such as BTX (benzene, toluene, xylene) solvents can be avoided, so strict VOC/emission requirements are observed. It is possible to meet the needs of the current polyurethane industry that requires management and exclusion of BTX.

[Benefits brought about by this manufacturing method]

The manufacturing method of this composition is an efficient manufacturing process that can use raw materials that are inexpensive and have varying quality, and even if a copolymer with the desired high molecular weight or strong foam stability is designed, there are no problems with foam control occurring during the manufacturing process. , because it can be easily solved, productivity is excellent, and manufacturing problems and quality problems directly related to industrial production costs can be comprehensively solved. For this reason, by using the polyether-polysiloxane block copolymer composition obtained by this production method, it is expected that it will be possible to sufficiently and stably distribute foam stabilizers containing the composition to the market and utilize them as high-performance raw materials.

As described above, the polyether-polysiloxane block copolymer composition of the present invention (including that obtained by the above production method) is particularly useful as a foam stabilizer used in the production of polyurethane foam, and is particularly useful as a surfactant and foam stabilizer for polyurethane foam. It can be used as is. Alternatively, it can be mixed into a premix solution for urethane foam and used as a system.

[Use of this composition]

Since the polyether-polysiloxane block copolymer composition according to the present invention has a silicone moiety and a polyether moiety with different hydrophilicities within the molecule, it can be used without particular limitation for the purposes of conventionally known polyether-polysiloxane block copolymers, and the interface It can be used as an activator, foam stabilizer, lubrication agent or softener for fibers, surface treatment or coating agent, and reactive raw material for other polymer materials without particular restrictions. In particular, the polyether-polysiloxane block copolymer composition of the present invention is useful as an industrial surfactant, and its formulations include paints, coating agents, building materials, hydrophilic imparting agents, surface treatment agents, foamable resin compositions, etc., and are not particularly limited. Additionally, due to its function as a surfactant, it is particularly useful as an additive for paints, an emulsifier, a solubilizer, and a foam stabilizer for polyurethane foam.

A particularly suitable use of the present composition is as a surfactant, a foam stabilizer for polyurethane foam, or a premix solution for polyurethane foam, and the use as a foam stabilizer will be described in more detail below. In addition, in this specification, polyurethane foam may be expressed as “polyurethane foam” or “foam.”

[Use as a purifying agent]

As described above, the polyether-polysiloxane block copolymer composition according to the present invention can be produced relatively easily, is less susceptible to quality influences originating from raw materials, and has excellent cost-in-use, so it can be used as a foamable resin, especially polyurethane foam. It can be suitably used as a foam control or foam stabilizing surfactant, especially as a foam stabilizing agent, in the production of .

In particular, when used as a foam stabilizer for polyurethane foam or as a premix solution for polyurethane foam, this composition is not limited to a simple bubble stabilizer, but is easy to control and design the open cell rate, has excellent homogeneity and stability of the premix solution, and is also used as a foam stabilizer. It has the advantage of being excellent in compatibility with various components in an emulsion composition for forming, and also having excellent foaming properties in microcellular applications and low-rebound foam applications.

[Composition comprising suitable components (A''), component (B') and component (N) and having a foam enhancing effect]

In general formula (3), component (A''), component (B'), and (N) satisfying the structural characteristics above, and (N) a monovalent carboxylic acid sodium salt having a carbon atom number in the range of 2 to 18.

, and the mass ratio of component (A''):component (B') is in the range of 20:80 to 60:40, and with respect to the sum of component (A'') and component (B'), the component The composition containing the sodium cation (Na ⁺ ) in (N) in the range of 0.6 to 6.7 wt.ppm is more effective than that of component (A'), component (B'), or a combination thereof at a specific mass ratio. The foam enhancing properties of the foaming agent are significantly improved. On the other hand, the amount of component (N) used has a critical significance, and if it is outside the above range, technical effects such as foam enhancement may not be sufficiently achieved. Specifically, to realize foam enhancing properties, component (N), which is a sodium salt, needs to be used in combination with components (A'') and (B') having appropriate structural characteristics, and if the amount used is below the above lower limit, There are cases where foam enhancement becomes insufficient, and if the above upper limit is exceeded, components tend to precipitate in the system beyond the limit of the compatibility balance of the formulation system, and sufficient foam enhancement may not be achieved.

The method for obtaining a composition having a foam enhancing effect according to the present invention is to limit the amount of component (N) used to the above range, and to use the raw material component (a1) and component (a2) that give component (A''). As long as it can be the same manufacturing method as described above, it is preferred, but is not limited to this manufacturing method. For example, when adding component (N), in the above step 1, instead of component (S), solvent (S3) one or more liquid compounds selected from saturated diol compounds having 3 to 9 carbon atoms ( For example, it can be dispersed in propylene glycol, etc.) and added to the manufacturing raw material system. In that case, the removal step of component (S) in step 2 is omitted, and the remaining raw material components are added while leaving the solvent (S3). A hydrosilylation reaction can be performed and is also preferred. In other words, the method of obtaining the composition having the foam enhancing effect described above may be a method that does not require the above steps 1 to 3, and as long as the above component composition is satisfied, the composition having the foam enhancing effect according to the present invention can be manufactured. There is no need to be specified by method.

[Polyurethane foam forming composition and polyurethane foam comprising this composition]

The polyurethane foam-forming composition and polyurethane foam according to the present invention contain the polyether-polysiloxane block copolymer composition of the present invention (including those obtained by the above production method), or are used as at least a part of the raw material. There are no restrictions on the type of foam, its characteristics, or the type of prescription applied.

In general, there are hard and soft polyurethane foams, and in detail, they are broadly divided into soft urethane foam, high-elasticity urethane foam, hard urethane foam, and special foam. For these details, for example, patent document 6 (International Publication No. 2016/166979) can be referred to. The composition and foam stabilizer according to the present invention are versatile, and even when mixed in various polyurethane foam formulations, they can realize excellent effects as foam stabilizers or benefits in industrial production.

In addition, as described above, the composition and foam stabilizer according to the present invention are easy to contain without BTX solvent and can be manufactured in large quantities at low cost, so they are suitable for obtaining low VOC/emission type polyurethane foam. In addition, it makes it easier for foam manufacturers or foam prescription (system) designers to manufacture foam or premix systems that do not contain BTX. In addition, in order to produce polyurethane foam with low VOC/emission or odor, it is desirable to add a non-volatile antioxidant to the polyol described later.

The polyether-polysiloxane block copolymer composition obtained by the production method of the present invention is a raw material in a polyurethane foam-forming composition containing the following ingredients: (d) It is suitable for use as a foam stabilizer.

(a) polyol,

(b) polyisocyanate,

(c) catalyst,

(d) antiseptic agent, and

(e) Optionally, foaming agents, foaming agents, diluents, chain extenders, cross-linking agents, water, non-aqueous foaming agents, fillers, reinforcing agents, pigments, dyes, colorants, flame retardants, antioxidants, and anti-ozone agents other than the component (d). , at least one additional ingredient selected from the group consisting of ultraviolet stabilizers, antistatic agents, disinfectants, and antibacterial agents,

Regarding the raw material components and usage amounts of the polyurethane foam-forming composition other than the foam stabilizer (d) above, known raw materials in the field can be selected and used, for example, Patent Document 6 (International Publication No. 2016) /166979) can refer to each ingredient listed.

In addition, the composition according to the present invention can be used as a foam stabilizer suitable for most polyurethane foams. The compounding amount is in the range of 0.1 to 10 parts by mass of the polyether-polysiloxane block copolymer (A') in the composition relative to 100 parts by mass of (a) polyol, preferably in the range of 0.5 to 5 parts by mass, and 1.0 to 1.0 parts by mass. 3.0 parts by mass is more preferable.

The polyurethane foam obtained using the "composition containing polyether-polysiloxane block copolymer (A')" according to the present invention may be rigid foam, semi-rigid foam, flexible foam, low-rebound foam, HR foam, or microcellular foam. there is. For details on these and their production process, refer to, for example, Patent Document 6 (International Publication No. 2016/166979), and at least part or all of the foam stabilizer described in Patent Document 6 can be used in the composition according to the present invention. By substituting a foaming agent, these polyurethane foams can be obtained. In addition, in the method for producing a foam stabilizer or a polyether-polysiloxane block copolymer composition described in Patent Document 3 (Japanese Patent Publication No. 08-156143) or Examples and Comparative Examples of International Publication No. 2021/131378, , the method obtained in the present invention (for example, adding an appropriate amount of the (N) component of the present invention before reaction and then reacting) is utilized to further improve foam performance in various polyurethane foams. It is arbitrarily possible to perform adjustment of the size.

In addition, the manufacturing method of the individual polyurethane foam can be appropriately selected, but in particular, the "composition containing polyether-polysiloxane block copolymer (A')" obtained by the manufacturing method of the present invention is described in the following patent publication or In the detailed description of the patent publication, especially in the Examples, etc., the polyurethane foam manufacturing method can be appropriately applied by substituting a silicone-based foam stabilizer, silicone surfactant, or silicone copolymer surfactant to achieve low VOC/emission of the foam. You can contribute. In addition, these detailed descriptions or disclosures of examples include disclosures regarding manufacturing equipment, and some of the components are further replaced by ordinary design changes by those skilled in the art, and the manufacturing conditions are appropriately changed according to changes in viscosity, etc. It may be.

· U.S. Patent Specification No. 7825205 (Japanese Patent Publication No. 5422115)

·Japanese Patent Publication No. 2014-210832

·Japanese Patent Publication No. 07-090102

·Patent Document 3 (Japanese Patent Publication No. (Hei) 08-156143), Japanese Patent Publication No. (Sho) 57-014797

·Patent Document 6 (International Publication No. 2016/166979)

· Method for producing polyurethane foam described in Japanese Patent Publication No. 2005-534770, Japanese Patent Publication No. 2005-534770, and Japanese Patent Publication No. 2010-535931;

· Manufacturing process of open cell polyurethane described in Japanese Patent Publication No. 2010-539280

· Sealing material containing urethane foam described in Japanese Patent Publication No. 2012-246397, Japanese Patent Publication No. 2009-265425, etc.

· Manufacture of urethane foam described in Japanese Patent Application Publication No. 2012-082273, Japanese Patent Application Publication No. 2010-247532, Japanese Patent Application Publication No. 2010-195870, Japanese Patent Application Publication No. 2002-137234, etc.

·Japanese Patent Publication No. 2010-500447, Japanese Patent Publication No. 2010-504391, Japanese Patent Publication No. 2010-538126, Japanese Patent Publication No. 2011-528726, Japanese Patent Publication No. 2013-529702 Manufacture of viscoelastic polyurethane foam described in etc.

In addition, the polyether-polysiloxane block copolymer composition obtained by the production method of the present invention can be used for known industrial purposes in (AB)n-type polyether-modified silicone other than polyurethane foam, such as a textile treatment agent and a softener for clothing. , it is optional to use it as a paint additive, etc.

[Disclosure and teaching of application of technical elements of the present invention to other hydrosilylation reaction processes]

Considering their functions, the sodium salt solution according to the present invention and the carboxylic acid salt used in the comparative examples described later are expected to have the same advantageous effects in a similar hydrosilylation reaction process. Therefore, with reference to the hydrosilylation reaction process according to the present invention, a general-purpose non-hydrolyzable polyether-modified silicone containing as a main component a structure in which polyether side chains and/or terminal chains are grafted to the organopolysiloxane main chain was prepared. The sodium salt solution according to the invention or other buffers examined in the comparative examples can be applied to these hydrosilylation reaction processes to improve production efficiency and production costs. Additionally, when producing these non-hydrolyzable polyether-modified silicones, before starting the hydrosilylation reaction, an appropriate amount of buffering agent is mixed into the raw material system in the same manner as the sodium salt solution according to the present invention, and then the solvent of the buffering agent is added to the strip. It can be produced by a method of starting a hydrosilylation reaction after removal by ping or the like, and the purpose of this description is to provide such teachings and suggestions.

Example

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples, but the present invention is not limited thereto. In addition, in the composition formula below, the Me ₃ SiO group (or Me ₃ Si group) is denoted as “M”, the Me ₂ SiO group is denoted as “D”, and the MeHSiO group is denoted as “M ^H ”, and the methyl group in M and D is expressed as a substituent. Units modified by R are expressed as M ^R and D ^R. In addition, IPA represents isopropanol, MeOH represents methanol, BDPG represents dipropylene glycol monobutyl ether, EO represents ethylene oxide or oxyethylene group, and PO represents propylene oxide or oxypropylene group.

<Reference data 1>

One of the characteristics of the composition and production method of the present invention is that it alleviates the influence of the quality of the raw materials used and achieves sufficient performance for practical use. The quality difference between BDPG suppliers is shown in Table 1, and the BDPG of companies H and L are different in purity, moisture content, acid value, etc.

[Table 1]: Quality differences by BDPG supplier

In the following experimental example, as a raw material component of the linear organopolysiloxane-polyether block copolymer,

(a1-1) Average composition formula CH ₂ =C(CH ₃ )CH ₂ -O(C ₂ H ₄ O) ₃₅ (C ₃ H ₆ O) ₂₇ -CH ₂ -C(CH ₃ )=CH ₂ Bismetalyl polyether (unsaturation 0.67 meq/g, hydroxyl value 0.8 mg-KOH/g)

(a1-2) Average composition formula CH ₂ =C(CH ₃ )CH ₂ -O(C ₂ H ₄ O) ₃₅ (C ₃ H ₆ O) ₂₇ -CH ₂ -C(CH ₃ )=CH ₂ Bismetalyl polyether (unsaturation 0.64 meq/g, hydroxyl value 2.1 mg-KOH/g)

(a1-3) Average composition formula CH ₂ =C(CH ₃ )CH ₂ -O(C ₂ H ₄ O) ₃₅ (C ₃ H ₆ O) ₂₇ -CH ₂ -C(CH ₃ )=CH ₂ Bismetalyl polyether (unsaturation 0.60 meq/g, hydroxyl value 3.8 mg-KOH/g)

(a1-4) Average composition formula CH ₂ =C(CH ₃ )CH ₂ -O(C ₂ H ₄ O) ₃₅ (C ₃ H ₆ O) ₂₇ -CH ₂ -C(CH ₃ )=CH ₂ Bismetalyl polyether (unsaturation 0.63 meq/g, hydroxyl value 0.7 mg-KOH/g)

(a1-5) Average composition formula CH ₂ =C(CH ₃ )CH ₂ -O(C ₂ H ₄ O) ₃₅ (C ₃ H ₆ O) ₂₇ -CH ₂ -C(CH ₃ )=CH ₂ Bismetalyl polyether (unsaturation 0.64 meq/g, hydroxyl value 1.2 mg-KOH/g)

*Note: (a1-1) to (a1-5) correspond to raw materials from different lots of bismetalyl polyether.

(a2-1) Methylhydrogenpolysiloxane represented by average composition M ^H D ₂₀ M ^H

Hydrosilylation reaction catalyst: Ligand solution of 1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane platinum complex (Pt concentration 0.43 wt%)

was used.

In addition, when using BDPG from the H company or the L company as the (B') component, it is expressed as "(B')BDPG (H company)" or "(B')BDPG (L company)."

[Light transmittance (T%) in each experimental example]

In the following experimental examples, the transparency (T%) of each obtained composition was measured by measuring the light transmittance at a wavelength of 580 nm using a spectrophotometer. The results are shown in the table as T%.

[Example 1]

Into a 500 mL reactor, 104.19 g of (a1-3) bismetalyl polyether (containing 500 ppm of natural vitamin E) and 0.15 g of a MeOH(S) solution of (N+S) 5 wt.% sodium acetate (N) were added. and heated to 60°C while stirring under nitrogen gas circulation. After the whole was mixed uniformly, MeOH was removed from the system by stripping for 30 minutes under the conditions of 60 to 80°C and 2 mmHg in the same reaction vessel. Return to pressure, add 45.81 g of (a2-1) methylhydrogenpolysiloxane and 150 g of (B') BDPG (L company) under stirring, add 0.08 mL of hydrosilylation reaction catalyst again, and add 60~ As a result of performing the reaction at 80°C for 5 hours, the reaction was almost complete. In this way, the average composition formula

[Tuesday 8]

(here, a=20, x1=35, y1=27, n≒6)

A nearly transparent liquid polyether-polysiloxane block copolymer composition containing at least a linear organopolysiloxane-polyether block copolymer containing the structural units represented by and BDPG in a ratio of 50:50, “1619 mm2/s, (25°C)” was obtained.

Since the molar ratio of the C=C group and Si-H group of the raw material was C=C/SiH=1.10, both ends of the copolymer are mainly blocked with polyether (=the terminal functional group is a methallyl group or hydroxyl group bonded to polyether) ) is thought to be. In addition, since some Si-H groups may cause dehydrogenation condensation with moisture or alcohols in the system during the reaction, some of the copolymer terminals contain a structure of SiOH or SiO-R ¹ (R ¹ is a residue such as BDPG). I think it does. In addition, the polyether portion here is a random adduct of ethylene oxide and propylene oxide. This is also the same in Comparative Examples 1-1 to 1-3.

[Comparative Example 1-1]

In the same manner as in Example 1, except that MeOH was not removed by stripping, 0.08 mL of hydrosilylation reaction catalyst was added, and the reaction was performed at 60-90°C for 6 hours, a translucent to almost transparent liquid was obtained. A polyether-polysiloxane block copolymer composition “1581 mm2/s, (25°C)” was obtained.

[Comparative Example 1-2]

In a 500 mL reactor, add 45.81 g of (a2-1) methylhydrogenpolysiloxane, 104.19 g of (a1-3) bismetalyl polyether (containing 500 ppm of natural vitamin E), and 150 g of (B') BDPG (L company). It was added and heated to 60°C while stirring under nitrogen gas circulation. 0.04 mL of hydrosilylation reaction catalyst was added, and the reaction was performed at 60-80°C for 3 hours. Next, a small amount of the reaction solution was collected and confirmed by the alkaline decomposition gas generation method, and the reaction was almost complete. In this way, the average composition formula

[Tuesday 9]

(where a=20, x1=35, y1=27, n<6)

An opaque liquid polyether-polysiloxane block copolymer composition "931 mm2/s, (( 25°C)” was obtained.

[Comparative Example 1-3]

As a raw material ingredient, 0.009 g of solid sodium acetate was added, heated to 56°C while stirring under nitrogen gas circulation, then 0.08 mL of hydrosilylation reaction catalyst was added, and the reaction was performed at 60 to 80°C for 6 hours. In the same manner as Comparative Example 1-2, the average composition formula

[Tuesday 10]

(here, a=20, x1=35, y1=27, n≒6)

Translucent liquid polyether-polysiloxane block copolymer composition "1528 mm2/s, (( 25°C)” was obtained.

[Example 2: Test to confirm reproducibility when lots of bismetalyl polyether of Example 1 are different]

Into a 500 mL reactor, 86.19 g of (a1-1) bismetalyl polyether (containing 500 ppm of natural vitamin E) and 0.12 g of a MeOH(S) solution of (N+S) 5 wt.% sodium acetate (N) were added. and heated to 60°C while stirring under nitrogen gas circulation. After the whole was mixed uniformly, MeOH was removed from the system by stripping for 40 minutes under the conditions of 60 to 80°C and 3 mmHg in the same reaction vessel. Return the pressure, add 38.81 g of (a2-1) methylhydrogenpolysiloxane and 125 g of (B') BDPG (L company) under stirring, add 0.06 mL of hydrosilylation reaction catalyst again, and stir at 60 to 90°C. As a result of carrying out the reaction for 6 hours, the reaction was almost complete. In this way, the average composition formula

[Tuesday 11]

(here, a=20, x1=35, y1=27, n≒6)

A substantially transparent liquid polyether-polysiloxane block copolymer composition containing at least a linear organopolysiloxane-polyether block copolymer containing the structural units represented by and BDPG in a ratio of 50:50, “1714 mm2/s, (25°C)” was obtained.

Since the molar ratio of the C=C group and Si-H group of the raw material was C=C/SiH=1.20, both ends of the copolymer are mainly blocked with polyether (=the terminal functional group is a methallyl group or hydroxyl group bonded to polyether) ) is thought to be. In addition, since some Si-H groups may cause dehydrogenation condensation with moisture or alcohols in the system during the reaction, some of the copolymer terminals contain a structure of SiOH or SiO-R ¹ (R ¹ is a residue such as BDPG). I think it does. In addition, the polyether portion here is a random adduct of ethylene oxide and propylene oxide. This is also the same in Comparative Example 3 and Comparative Example 4-1.

[Example 3: Test to confirm reproducibility of Example 2]

In a 500 mL reactor, 86.70 g of (a1-4) bismetalyl polyether (containing 500 ppm of natural vitamin E), (N+S) 0.12-0.13 g of MeOH(S) solution of 5 wt.% sodium acetate (N). was added and heated to 60°C while stirring under nitrogen gas circulation. After the whole was mixed uniformly, MeOH was removed from the system by stripping for 30 minutes under the conditions of 60 to 80°C and 7 to 8 mmHg in the same reaction vessel. Return the pressure, add 38.31 g of (a2-1) methylhydrogenpolysiloxane and 125 g of (B') BDPG (L company) under stirring, add 0.06 mL of hydrosilylation reaction catalyst again, and stir at 70 to 80°C. As a result of performing the reaction for 3 hours, completion of the reaction was confirmed. In this way, the average composition formula

[Tuesday 12]

(here, a=20, x1=35, y1=27, n≒6)

A nearly transparent liquid polyether-polysiloxane block copolymer composition containing at least a linear organopolysiloxane-polyether block copolymer containing the structural units represented by and BDPG in a ratio of 50:50, “1634 mm2/s, (25°C)” was obtained.

Since the molar ratio of the C=C group and Si-H group of the raw material was C=C/SiH=1.15, both ends of the copolymer are mainly blocked with polyether (=the terminal functional group is a methallyl group or hydroxyl group bonded to polyether) ) is thought to be. In addition, since some Si-H groups may cause dehydrogenation condensation with moisture or alcohols in the system during the reaction, some of the copolymer terminals contain a structure of SiOH or SiO-R ¹ (R ¹ is a residue such as BDPG). I think it does. In addition, the polyether portion here is a random adduct of ethylene oxide and propylene oxide.

[Comparative Example 2]

Into a 1 L reactor, 75.25 g of (a2-1) methylhydrogenpolysiloxane, 174.75 g of (a1-2) bismetalyl polyether, 250 g of (B') BDPG (H company), and 0.25 g of natural vitamin E were added, It was heated to 80-90°C while stirring under nitrogen flow. 0.56 g of hydrosilylation reaction catalyst was added, and the reaction was performed for 2.5 hours. Next, a small amount of the reaction solution was collected and confirmed by the alkaline decomposition gas generation method (the remaining Si-H group was decomposed with an ethanol/aqueous solution of KOH, and the reaction rate was calculated from the volume of generated hydrogen gas), and the reaction was complete. . In this way, the average composition formula

[Tuesday 13]

(here, a=20, x1=35, y1=27, n≒6)

A substantially transparent liquid polyether-polysiloxane block copolymer composition containing at least a linear organopolysiloxane-polyether block copolymer containing the structural units represented by and BDPG in a ratio of 50:50, “1680 mm2/s, (25°C)” was obtained.

In addition, although the average composition formula is simply expressed, the molar ratio of the C=C group and Si-H group of the raw material is C=C/SiH=1.18, so both ends of the copolymer are blocked with polyether (= terminal functional group) is a methallyl group or hydroxyl group bonded to polyether). In addition, since some of the Si-H groups may cause dehydrogenation condensation with moisture or alcohols in the system during the reaction, some of the copolymer terminals have the structure of SiOH or SiO-R ¹ (R ¹ is a residue such as BDPG or IPA). It is thought to include. In addition, the polyether portion here is a random adduct of ethylene oxide and propylene oxide.

[Comparative Example 3: Test to confirm reproducibility of Comparative Example 1-1]

In a 500 mL reactor, (a2-1) 38.81 g of methylhydrogenpolysiloxane, (a1-1) 86.19 g of bismetalyl polyether (containing 500 ppm of natural vitamin E), (B') BDPG (L company) 125 g, (N+S) 0.12 to 0.13 g of a 5 wt.% sodium acetate (N) MeOH(S) solution was added and heated to 46°C while stirring under nitrogen flow. 0.06 mL of hydrosilylation reaction catalyst was added, and the reaction was performed at 60-80°C for 4 hours. A small amount of the reaction solution was collected and confirmed by the alkaline decomposition gas generation method, and the reaction was almost complete. In this way, the average composition formula

[Tuesday 14]

(here, a=20, x1=35, y1=27, n≒6)

A translucent to almost transparent liquid polyether-polysiloxane block copolymer composition containing at least a linear organopolysiloxane-polyether block copolymer containing the structural units represented by and BDPG in a ratio of 50:50, 「1533 mm2/ s, (25°C)” was obtained.

[Comparative Example 4-1: Test to confirm reproducibility of Comparative Example 3]

In a 500 mL reactor, (a2-1) 38.30 g of methylhydrogenpolysiloxane, (a1-4) 86.70 g of bismetalyl polyether (containing 500 ppm of natural vitamin E), (B') BDPG (L company) 125 g, (N+S) 0.12 to 0.13 g of a 5 wt.% sodium acetate (N) MeOH(S) solution was added and heated to 51°C while stirring under nitrogen flow. After adding 0.06 mL of hydrosilylation reaction catalyst and performing the reaction at 50-80°C for 3.5 hours, completion of the reaction was confirmed. A translucent to almost transparent liquid polyether-polysiloxane block copolymer composition “1383 mm2/s, (25°C)” was obtained.

[Comparative Example 4-2]

In a 500 mL reactor, add 43.56 g of (a2-1) methylhydrogenpolysiloxane, 81.45 g of (a1-4) bismetalyl polyether (containing 500 ppm of natural vitamin E), and 125 g of (B') BDPG (L company). It was added and heated to 45°C while stirring under nitrogen flow. 0.06 mL of hydrosilylation reaction catalyst was added, and the reaction was performed at 45-80°C for 4.5 hours, and the reaction was almost complete. In this way, the average composition formula

[Tuesday 15]

(where a=20, x1=35, y1=27, n>6)

Almost transparent liquid polyether-polysiloxane block copolymer composition "7300 cP, (25 ℃)” was obtained.

[Evaluation criteria for each experiment]

The hydrosilylation reaction process for providing a linear organopolysiloxane-polyether block copolymer was evaluated as follows, taking into account differences in raw materials and reaction systems.

Regarding hydrosilylation reactivity (hereinafter sometimes simply referred to as “reactivity”), Example 1 is set to “A”,

“positive” for better reactivity;

Especially in case of excellent reactivity, “Woo”

It was evaluated as .

In addition, regarding the viscosity (rate of change) of the obtained composition, the upper and lower viscosity values in each experimental example using the same bismetalyl polyether (1 to 3) as "0%" (= standard) are expressed as %. It is shown in the table. However, in Comparative Example 2, since the BDPG source was different, the viscosity change rate was not evaluated.

[Summary]

The results of a series of experiments are shown in Table 2. Except for Comparative Example 2 in which the BDPG raw material was different and Comparative Example 4-2 in which the C=C/Vi ratio was different, for easy comparison, the same lot of bismetalyl polyether raw material was used and the C=C/Vi ratio was the same in Examples. /Comparative examples are summarized in the table.

First, Examples 1 to 3 used BDPG from Company L, which is relatively inexpensive and has a somewhat high acid value, as a raw material. Even when bismetalyl polyether raw materials from any lot were used, BDPG from Company H, which is expensive, was used as a raw material. When compared with Comparative Example 2, which is a reference product, a polyether-polysiloxane block copolymer composition with almost comparable reactivity, viscosity, and transparency (i.e., light transmittance T%) could be prepared. In other words, by using the production method according to the present invention, side reactions are effectively suppressed, a composition with a high viscosity sufficient for practical use, a higher degree of polymerization of the copolymer, closer to the designed structure, and a composition with sufficient quality for practical use can be obtained. Could know.

On the other hand, Comparative Example 2 does not contain a buffer or sodium acetate and roughly corresponds to the contents of Reference Example 1-1 of International Publication No. 2016/166979 (Patent Document 6). By using BDPG from Company H, which has a low acid value, high purity, and is expensive, it was possible to obtain a composition with the molecular weight of a copolymer and a practical viscosity and appearance. However, since BDPG from Company H is expensive, this composition could be manufactured at a low price. It is difficult to provide a stable supply to the market.

On the other hand, when comparing Examples/Comparative Examples using the same bismetalyl polyether raw material and having the same C=C/Vi ratio, the composition according to the Examples obtained by the production method of the present invention has a higher viscosity than the Comparative Example. , side reactions were suppressed, and transparency was excellent. These effects are believed to be due to the fact that the buffer component is finely dispersed in the raw materials and the unnecessary dispersion medium is removed in advance, thereby efficiently neutralizing the acidic substance.

On the other hand, in Comparative Examples 1-1, 2-1, and 3-1 in which stripping was not performed, the viscosity and transparency did not reach those of the compositions according to the examples, and Comparative Example 1-2 lacked a buffering agent. In Comparative Example 1-3 where bare solid was added, the viscosity and transparency were even lower than those in these comparative experiments. Therefore, it was confirmed that the technical effects of the present invention, including suppression of side reactions, could not be achieved if the production method of the present invention was not used and the low-priced BDPG of Company L was used. In addition, these results are common results when the lot of bismetalyl polyether raw material is the same, and good reproducibility was confirmed.

Comparative Example 4-2 sets the true value of the molar ratio of the C=C group and Si-H group of the raw material: C=C/SiH to a condition close to 1.0 (0.95 when simply calculated from the analysis results of each raw material), thereby producing low-cost L Using our company's BDPG, the goal is to obtain a composition with high molecular weight (high viscosity) even under unfavorable conditions in the absence of a buffering agent.

In this experimental example, the composition with the highest viscosity was obtained among the series of experimental examples, but compared to each example and Comparative Example 2, which is a reference product, the viscosity was very high. When this method was used for commercial production, the composition after synthesis It was strongly suggested that large viscosity deviations occurred. Additionally, from the standpoint of production management, it is difficult to carry out a strict C=C/SiH design for each production according to the raw materials, and there is an inherent problem of deteriorating industrial productivity and production costs. In addition, the results of Comparative Example 4-2 show that even if strict production control is performed, there is a large deviation in the viscosity of the product due to quality fluctuations depending on the lot of raw materials or storage conditions, weighing errors, and minor changes in manufacturing conditions. Since this strongly suggests that it is easy to produce products that deviate from quality standards, the production method that strictly controls the true value of C=C/SiH instead of the production method of the present invention has the purpose of supplying this composition to the market stably at a low price. It is not suitable for achieving this, and in particular, there is strong concern about the lack of industrial productivity at stable quality standards.

*) This is a comparison standard product made with BDPG from Company H as a raw material, and was not subject to evaluation of viscosity change rate.

**) The viscosity deviation is large compared to other experimental examples, raising concerns about stable industrial productivity.

[Examples 4-1 to 4-3, Example 5 and others: Effective range of addition amount [ppm] of sodium acetate to BDPG]

In order to confirm the effective range of the addition amount [ppm] of sodium acetate to BDPG, in the production method of the present invention, the addition amount of sodium acetate was changed to prepare a composition containing a linear organopolysiloxane-polyether block copolymer. , the relationship between the added amount of sodium acetate (ppm) and the viscosity of the resulting composition is shown in Figure 1. In addition, in these examples, etc., unlike the case of Examples 1 to 3, all raw materials except the hydrosilylation reaction catalyst are first introduced into a flask (reaction vessel), and after mixing, they are removed by stripping. After performing the MeOH treatment, the hydrosilylation reaction catalyst was added to start the reaction. In addition, BPDG manufactured by L Company is used as the raw material, and bismetalyl polyether (a1-4) or (a1-2) is used.

[Standard product and target level]

Here, Example 4-1 and Example 5, which gave compositions with good viscosity, were used as reference products (±0%), and it was considered that it was sufficient for practical use if the viscosity reduction rate was within 5% of these standard products, and the viscosity The reduction rate - 5% is indicated by the solid line in Figure 1 as the target level.

[Example 4-1]

In a 1 L reactor, (a2-1) 127.12 g of methylhydrogenpolysiloxane, (a1-4) 272.88 g of bismetalyl polyether (containing 500 ppm of natural vitamin E), (B') 400 g of BDPG (L company), (N+S) 0.16 g of a MeOH(S) solution of 5 wt.% sodium acetate (N) (20 wt.ppm relative to BDPG as sodium acetate) was added, and heating was started while stirring under nitrogen flow. MeOH was removed from the system by stripping for 30 minutes under conditions of 75-80°C and 65-90 mmHg. The pressure was restored, 0.21 mL of hydrosilylation reaction catalyst was added, and aging was performed at 80-85°C for 3.5 hours to complete the reaction. In this way, the average composition formula

[Tuesday 16]

(here, a=20, x1=35, y1=27, n≒6)

Light yellow transparent liquid polyether-polysiloxane block copolymer composition containing at least a linear organopolysiloxane-polyether block copolymer containing the structural units represented by and BDPG in a ratio of 50:50, “1862 mm2/s, (25°C)” was obtained.

Since the molar ratio of the C=C group and Si-H group of the raw material was C=C/SiH=1.10, both ends of the copolymer are mainly blocked with polyether (=the terminal functional group is a methallyl group or hydroxyl group bonded to polyether) ) is thought to be. In addition, since some Si-H groups may cause dehydrogenation condensation with moisture or alcohols in the system during the reaction, some of the copolymer terminals contain a structure of SiOH or SiO-R ¹ (R ¹ is a residue such as BDPG). I think it does. In addition, the polyether portion here is a random adduct of ethylene oxide and propylene oxide. This is common to Examples 4-2 to 4-3 and Comparative Example 5 below.

[Example 4-2]

Instead of 0.16 g of a 5 wt.% MeOH solution of sodium acetate,

The experiment was performed almost identically to Example 4-1, except that 0.32 g of a 5 wt.% MeOH solution of sodium acetate (40 wt.ppm for BDPG as sodium acetate) was used. A light yellow transparent liquid polyether-polysiloxane block copolymer composition “1891 mm2/s, (25°C)” was obtained.

[Example 4-3]

Instead of 0.16 g of a 5 wt.% MeOH solution of sodium acetate,

The experiment was performed almost identically to Example 4-1, except that 0.80 g of a 5 wt.% MeOH solution of sodium acetate (100 wt.ppm for BDPG as sodium acetate) was used. A light yellow transparent liquid polyether-polysiloxane block copolymer composition “1862 mm2/s, (25°C)” was obtained.

[Comparative Example 5: No use of sodium acetate (=0 wt.ppm)]

In a 1 L reactor, add 124.69 g of (a2-1) methylhydrogenpolysiloxane, 267.66 g of (a1-4) bismetalyl polyether (containing 500 ppm of natural vitamin E), and 393 g of (B') BDPG (L company). It was added and heated to 68°C while stirring under nitrogen gas circulation. 0.21 mL of hydrosilylation reaction catalyst was added, and the reaction was performed at 70-85°C for 4 hours, and the reaction was complete. In this way, the average composition formula

[Tuesday 17]

(where a=20, x1=35, y1=27, n<6)

A light yellow transparent liquid polyether-polysiloxane block copolymer composition containing at least a linear organopolysiloxane-polyether block copolymer containing the structural units represented by and BDPG in a ratio of 50:50, “624 mm2/s, (25°C)” was obtained.

[Example 5]

In a 3 L reactor, (a2-1) 403.92 g of methylhydrogenpolysiloxane, (a1-5) 946.08 g of bismetalyl polyether (containing 500 ppm of natural vitamin E), (B') BDPG (L company) 1350 g, (N+S) 2.70 g of a MeOH(S) solution of 2 wt.% sodium acetate (N) (40 wt.ppm relative to BDPG as sodium acetate) was added, and heating was started while stirring under nitrogen flow. MeOH and moisture were removed from the system by stripping for 1 hour under conditions of 55 to 85°C and 15 to 20 mmHg. The pressure was returned, 0.31 ml of hydrosilylation reaction catalyst was added, and aging was performed for 2.5 hours at 55-85°C, and the reaction was completed. In this way, the average composition formula

[Tuesday 18]

(here, a=20, x1=35, y1=27, n≒6)

A light yellow transparent liquid polyether-polysiloxane block copolymer composition containing at least a linear organopolysiloxane-polyether block copolymer containing the structural units represented by and BDPG in a ratio of 50:50 "1552 mm2/s, (25°C)” was obtained.

Since the molar ratio of the C=C group and Si-H group of the raw material was C=C/SiH=1.18, both ends of the copolymer are mainly blocked with polyether (=the terminal functional group is a methallyl group or hydroxyl group bonded to polyether) ) is thought to be. In addition, since some Si-H groups may cause dehydrogenation condensation with moisture or alcohols in the system during the reaction, some of the copolymer terminals contain a structure of SiOH or SiO-R ¹ (R ¹ is a residue such as BDPG). I think it does. In addition, the polyether portion here is a random adduct of ethylene oxide and propylene oxide. This is common in Comparative Example 6.

[Comparative Example 6: Excess sodium acetate (=200 wt.ppm)]

Instead of 2.70 g of a 2 wt.% MeOH solution of sodium acetate,

Almost the same as Example 5, except that 13.5 g of a 2 wt.% MeOH solution of sodium acetate (200 wt.ppm for BDPG as sodium acetate) was used, and the stripping time of MeOH or moisture was set to 3 hours. Then, an experiment was performed. A light yellow transparent liquid polyether-polysiloxane block copolymer composition “1193 mm2/s, (25°C)” was obtained.

[Summary]

Table 3 below summarizes the experimental results.

*It was treated as a reference product in a series of experiments, and a viscosity change rate of -5% was set as the “target level” when the same bismetalyl polyether raw material was used.

In Examples 4-1 to 4-3 and Example 5, a composition having a viscosity sufficient for practical use could be obtained even when BDPG manufactured by L Company, which had a somewhat high acid value, was used. On the other hand, in Comparative Example 5 in which sodium acetate was not used as a buffering agent, side reactions could not be sufficiently suppressed, and only a low-viscosity product was obtained. In addition, although the amount was sufficient to neutralize the acidic substances in BDPG manufactured by L Company, the viscosity of the composition decreased in Comparative Example 6. This suggests that excessive amounts of sodium acetate may actually cause side reactions, and the amount added has technical significance. Based on the graph of FIG. 1 above, the amount of sodium acetate added that gives the obtained polyether-polysiloxane block copolymer composition a viscosity change rate of an absolute value smaller than the target level (viscosity change rate of -5% with respect to the reference product) is sodium acetate. In ion conversion, it was in the range of 3.8 to 43 ppm for BDPG. Based on the performance values, the upper and lower limits of the addition amount of the specific sodium salt according to the present invention were determined.

This is a summary of the analysis results by ²⁹ SiNMR of the samples of Example 2, Example 3, Comparative Example 3, and Comparative Example 4-1 related to the present invention, and the polyether-polysiloxane block copolymer (A'), which is the main component in the obtained composition, This shows average structural information. In addition, the average structure (substance amount ratio) in Table 4 is expressed as a molar ratio where the sum of the terminal groups of component (A') is set to 2.

[Table 4]: ²⁹ SiNMR analysis results of Example 2, Example 3, Comparative Example 3, and Comparative Example 4-1

R=-CH ₂ CHMeCH ₂ O(EO) _x1 (PO) _y1 -,OX=OH or alkoxy group

²⁹ By SiNMR, the difference in the average chemical structure of the main components of the Example and Comparative Example could not be clearly detected, and both appear to have been synthesized approximately normally.

This is a summary of the results of GPC (detector: refractometer) analysis using chloroform eluent for the samples of Example 2, Example 3, Comparative Example 3, and Comparative Example 4-1 related to the present invention. Here, the average molecular weight is polystyrene conversion value.

[Table 5]: GPC data of each sample above (design degree of polymerization of copolymer n=6)

From the GPC analysis results, all four samples were copolymers with a molecular weight exceeding 30,000, which is considered the standard for performing as a foam stabilizer for polyurethane microcellular foam, and the polyether raw material containing unreacted methallyl groups at both ends was obtained. It was confirmed that the ratio was also small. However, in Comparative Example 4-1, the peak of the copolymer slightly shifted toward the low molecular weight side compared to the other three samples, and the residual proportion of unreacted polyether was also large.

[Example 6]

For methylhydrogenpolysiloxane, bismetalyl polyether, and (B')BDPG (L Company), the same lot as Example 5 was used, and the total amount of main raw materials was approximately 3.5 t using the manufacturing procedure according to Example 5. The input amount of each raw material was scaled up and a factory production test was performed with a 4 m ³ reactor. The factory's production system seemed difficult to maintain as clean conditions as the laboratory experiment, so the hydrosilylation reaction took a lot of time, but when the reaction was almost complete, it cleared the viscosity target value despite being a light yellow transparent liquid. Afterwards, filtration was performed using a zeta potential type adsorption filtration filter. A light yellow transparent liquid [light transmittance T% (580 nm) = 97] polyether-polysiloxane block copolymer composition “1557 mm2/s, (25°C)” was obtained.

[Example 7: Filtrated product of Example 2]

100 g of the polyether-polysiloxane block copolymer composition obtained in Example 2 was filtered through a zeta potential type adsorption filtration filter with a diameter of 90 mm to obtain 80.3 g of a pale yellow transparent uniform filtrate. As a result, the light transmittance T% (580 nm) of the composition was improved from 78% before filtration to 97% after filtration.

[Additional performance evaluation as a purifier and significance of the filtered product]

Example 6, which is an industrial-scale filtration product, and Example 7, which is a filtrated product of Example 2 described above, were prepared, and a "foam retention test" using a homodisper mixer described later was performed, and the compositions related to Examples, etc. A more detailed performance evaluation was performed. Additionally, the presence or absence of any change in appearance was confirmed.

[Bubble retention test]

For the samples of Examples 2 and 7, Example 6 and Comparative Example 4-2, the foam-retaining ability as a surfactant was tested using a homodisper mixer according to the following procedures. In addition, in order to increase the stirring power, the direction of the saw blade of the disper was fixed in the opposite direction to the rotation direction.

[order]

1. Add 30 g of foam purifier sample to a clean 200 mL wide-mouth glass bottle and leave to stand.

2. Measure and record the height of the liquid level of the sample. A line is drawn with an oil-based marker pen along the meniscus, and the height of the upper end of the line is treated as the initial height of the liquid surface. Approximately, the lower end of the line is 18 mm from the bottom of the bottle, and the top of the stopper is 20 mm from the bottom of the bottle.

3. Dip the saw blade of the Homo Disper into the center of the liquid, and set the height to a slightly higher position so that the saw blade does not touch the bottom of the glass bottle.

4. Fix the glass bottle containing the sample with a clamp.

5. Stir by homodisper at 3000 rpm for 2 minutes.

6. When the stirring stops, move the saw blade to a position about 1 cm higher so that it does not touch the foamed liquid, fix it, and idle for a short time to remove the liquid attached to the saw blade.

7. Disassemble the glass bottle, mark the height of the bubble (top) with a permanent marker pen, and find the difference [cm] from the initial height. Depending on the size of this value, the good or bad foam retention was judged.

Note) Steps 6 to 7 were performed in a short time of about 30 seconds. However, it was found through observation after the test that the height of the bubbles generated hardly changed for at least 3 to 5 minutes.

For the above samples, long-term storage stability at room temperature was evaluated by measuring appearance and light transmittance.

Additionally, Na [ppm] was quantified for the above sample using the “Acid Decomposition-ICPMS method.” The analysis value was obtained as the average value of two measurements.

Table 6 below summarizes the test results for foam retention, storage stability, and Na content.

[Table 6]: Relationship between foam retention, storage stability, and Na content of samples

*Analysis value quantified by ICPMS method

From Table 6, the composition containing the "polyether-polysiloxane block copolymer (A') obtained by the production method of the present invention does not cause defects such as separation even without filtration and has the properties of a uniform liquid. However, an unexpected benefit was discovered in that filtration further improved the stability of the appearance and even improved foam retention (Example 7). Comparative Example 4-2, in which no sodium salt was added, had a high viscosity and generally had advantageous properties as an anti-foaming agent, but the same effect could not be confirmed. On the other hand, Example 7, in which the content of sodium ions was reduced by filtration, had excellent foam retention even compared to Example 2 containing the same polymer component, and the sodium content [ppm] in the composition and the polyether-polysiloxane block copolymer The relationship between the foam holding power [cm] of the composition is plotted in Figure 2.

In Figure 2, the target value of foam retention force was set to 4.0 cm. As a result of estimating from this graph, the range of sodium content for the foam retention of the polyether-polysiloxane block copolymer composition to reach the target level is for the composition (in particular, the sum of component (A'') and component (B)). It was found to be approximately 0.6 to 6.7 wt.ppm. This range has critical significance, and unlike the sodium content in the production method, by controlling the sodium content in the final composition to the above range, a new function of foam enhancement, which is completely different from the effect as a buffer, can be realized. It has been confirmed.

Additionally, the samples of Example 7 and Comparative Example 4-2 were mixed with polypropylene glycol (average molecular weight 425, abbreviated as PPG-425), a type of polyether polyol, to prepare a premix solution. At this time, since the mass ratio of sample:PPG = 6.0 g: 24.0 g, the concentration of polyether-polysiloxane block copolymer (A') in the solution was 10 wt.%. These are referred to in order as Example 8 and Comparative Example 7.

According to the [Bubble Retention Test] and [Procedure] above, the foam retention properties of these premix solutions were tested. At this time, PPG-425 (30 g) without anti-foaming agent was tested together as a reference sample. The results are summarized in Table 7 below. The foam volume increase rate [%] in the table was calculated based on the data of Comparative Example 7 using the sample of Comparative Example 4-2 (set as zero).

[Table 7]: Foam retention capacity of premix solution

Comparative Example 7 used the foam stabilizer composition of Comparative Example 4-2, which has an extremely high viscosity and is generally considered to have advantageous properties as a foam stabilizer, and was confirmed to have practically effective performance in this test. However, the premix solution of Example 8, which used the much lower viscosity foam stabilizer of Example 7, had superior foaming and foam retention properties compared to Comparative Example 7, and contained an extremely limited amount of sodium salt of monovalent carboxylic acid. In the polyether-polysiloxane block copolymer composition, a foam enhancing effect greater than the viscosity or molecular weight of the polymer has been achieved.

[Examples 9 to 11: Composition containing component (C) and compatibility evaluation thereof]

In the following experiment, the compatibility of the sample of Example 6 (hereinafter referred to as “Ex sample” or “Ex”) with various polyether polyols and polyglycol derivatives was investigated. Those with excellent compatibility with Ex samples can be used as a diluent for the "composition containing polyether-polysiloxane block copolymer (A')" obtained by the production method of the present invention, and the foam stabilizer for polyurethane foam according to the present invention can be configured. Alternatively, it can be said to be suitable as a base polyol for a premix solution for urethane foam containing the composition according to the present invention. As another effect of these diluents, it is possible to control the hydroxyl value of the foam stabilizer, thereby controlling the influence on the pre-designed strength or crosslink density of the polyurethane foam. Furthermore, it is effective in controlling the breathability and cell size of the foam.

Here, the position settings for Examples 9 to 11 are as follows.

Example 9: Compatibility evaluation test of Ex sample and polyether monool (C1)

Example 10: Compatibility evaluation test of Ex sample and polyether diol (C2)

Example 11: Compatibility evaluation test of Ex sample and polyether triol (C3)

[Evaluation test of compatibility]

Inject the Ex sample and component (C) into a 25 ml screw tube at three mixing ratios of Ex/C = 5.0 g/5.0 g, 2.0 g/8.0 g, and 0.5 g/9.5 g so that the total is 10 g. Compatibility test was performed in the following order: visual confirmation of the liquid appearance.

[order]

1. Place a stopper on the screw pipe, shake well up and down about 10 times to mix, and leave in a constant temperature bath at 50°C for 10 to 15 minutes to roughly remove air bubbles.

2. After recording the appearance at 50℃, take out the screw tube and return it to room temperature.

3. After recording the appearance at room temperature, samples with a cloudy appearance and non-uniform appearance are left to stand overnight and observed. Samples that have a translucent to transparent appearance and are visually uniform are placed in a refrigerator at 5°C for 1 to 2 hours and observed for changes in appearance.

4. After recording the appearance of the sample placed in the refrigerator at 5℃, take out the screw tube and return it to room temperature. Also, check whether the appearance at room temperature is significantly different from the appearance record (room temperature) in step 3.

5. Record the appearance of the white-clouded sample in step 3 after standing overnight.

In addition, the evaluation of appearance was made according to the following criteria.

*The intermediate case between the two is indicated by “~”.

◎: Transparent uniform liquid

○: Translucent to almost transparent uniform liquid

△: Translucent uniform liquid

×: Opaque, cloudy liquid

<Example 9: Compatibility evaluation test with polyether monool (C1)>

Table 8 shows the results of evaluating the compatibility of the Ex sample with polyether monool (C1) having the structure and molecular weight shown in Table 8 below.

Note) Regarding the structure of C1 in Table 8, the EO chain and PO chain are written in block form for simplicity, but in reality, they are random copolymers.

<Example 10: Compatibility evaluation test with polyether diol (C2)>

Table 9 shows the results of evaluating the compatibility of the Ex sample with polyether diol (C2) having the structure and molecular weight shown in Table 9 below.

Note) Regarding the structure of C2 (Comparative Example 9-1) in Table 9, the EO chain and PO chain are expressed in block form for simplicity, but in reality, they are random copolymers.

<Example 11: Compatibility evaluation test with polyether triol (C3)>

Table 10 shows the results of evaluating the compatibility of the Ex sample with polyether triol (C3) having the structure and molecular weight shown in Table 10 below.

Note) The structure of C3 in Table 10 (Comparative Example 10-1) is an EO/PO random copolymer.

[About ingredient (C1)]

As shown in Table 8, when polyether monool is used as a diluent, in the case of a single addition polymer of PO (propylene oxide), compatibility with component (A') is approximately maintained even when the added mole number is close to 40 and the chain is long. and the stability of the mixed solution was good. On the other hand, in the case of an addition copolymer of EO (ethylene oxide) and PO, wt.% of EO = 50 was set constant and the molecular weights were compared at 500, 1000, and 3000. As a result, the total number of added moles of EO exceeded 30. In one final case, stability deteriorated dramatically. In addition, since the single addition polymer of EO is completely incompatible with component (A'), it was also revealed that a polymerization unit of PO is required in the structure of polyether monool.

From these results, the upper limit of the added mole number of EO when polyether monool is used as a diluent is estimated to be around 20, the upper limit of the added mole number of PO is around 50, and the upper limit of the wt.% of EO in the structure is estimated to be around 60. . In the experience of the present inventors, when the wt.% of EO of polyether monool is 70 or more, the solidification point increases, and under low temperatures in winter, it tends to generate sediment or a cloudy appearance, so in the present invention, polyether monool The upper limit of wt.% of EO when using monool as a diluent was set to around 60.

[About ingredient (C2)]

As shown in Table 9, when polyether diol is used as a diluent, in the case of a single addition polymer of PO (propylene oxide), compatibility with component (A') is very good even if the added mole number is a long chain around 35. And the stability of the mixed solution was also good. When the added mole number of PO is around 70, a decrease in compatibility is confirmed, but under the condition of high (A') component concentration (Ex/C2=50/50), the stability of the mixed solution is within the acceptable range, and it is thought that it can also be used as an anti-foaming agent. do. On the other hand, an addition copolymer of EO (ethylene oxide) and PO with EO wt.% = 50 and a molecular weight of 1750 was tested, and it was found that the stability was extremely poor.

From these results, the upper limit of the added mole number of EO when using polyether diol as a diluent was estimated to be around 10, the upper limit of the added mole number of PO was around 70, and the upper limit of the wt.% of EO in the structure was estimated to be around 30.

[About ingredient (C3)]

As shown in Table 10, compared to polyether diol or polyether monool, polyether triol has somewhat lower compatibility with the composition according to the present invention mainly composed of component (A') and component (B'). A downward trend was confirmed. In the case of polyether triol, which is a single addition polymer of PO, compatibility was insufficient at a mixing ratio of Ex/C3=20/80. However, under the condition of high concentration of (A') component, Ex/C3 = 50/50, the stability of the mixed solution was within the acceptable range, and it is believed that it can be used as an anti-foaming agent. In addition, even under the low concentration of (A') component of Ex/C3 = 5/95 (assuming the situation of a premix solution for polyurethane foam), the stability of the mixed solution was within the acceptable range. On the other hand, an addition copolymer of EO (ethylene oxide) and PO with EO wt.% = 50 and a molecular weight of 2800 was tested, and it was found that the stability was extremely poor.

From these results, when using polyether triol as a diluent, the upper limit of wt.% of EO in the structure was estimated to be around 20, and the range of the average molecular weight was estimated to be approximately 500 to 4500.

[General]

In the case of using a low-cost and high acid value glycol ether compound (B') as a raw material by using a production method including an improved hydrosilylation reaction process including steps 1 to 3 of the present invention according to the above examples, etc. The production efficiency of the composition containing the polyether-polysiloxane block copolymer (A') and the foam stabilizer using the same is significantly improved, and its quality problems can be solved, and its technical effect is Even when raw materials such as bismetalyl polyether were used, good reproducibility was confirmed.

In particular, according to the present invention, even if an inexpensive glycol ether compound (B') is used as a raw material, a suitable buffer component that can achieve the same quality as when using a very low acid value and expensive glycol ether compound (B') Alternatively, the buffer system, the range of the appropriate addition amount of the buffer agent, and the appropriate manufacturing method for the (AB)n-type polyether-modified silicone composition using the buffer agent are provided.

Furthermore, according to the present invention, in the case where the composition contains a polyether-polysiloxane block copolymer (A'') of a specific structure and the contents of the glycol ether compound (B') and sodium salt are within an extremely limited range, the conventional buffering agent It was confirmed that a composition with foam enhancing properties that was different from the technical effect of sodium salt was obtained. Likewise, sufficient knowledge for practical purposes was obtained regarding the appropriate combination and compatibility relationship between the composition according to the present invention and component (C).

According to the above experimental results, the polyether-polysiloxane block copolymer composition, and its improved production, can be supplied to the market in a stable and large quantity at low cost by solving the conventional quality and process problems by simple means through the present invention. It is understood and expected that a method, a composition excellent in cost-in-use and foam enhancement properties, and a foam stabilizer for polyurethane foam comprising the same can be realized.

Claims (15)

Process 1:
At least
(a1) General formula (1):
[Tuesday 1]

(In the formula, x is a number from 2 to 4, y represents a number in which the molecular weight of the _polyether portion represented by ( _C Represents a monovalent hydrocarbon group having 2 to 8 carbon atoms having a C group, and the polyether portion contains at least 1 oxypropylene group)
A polyether containing alkenyl groups at both ends, and
(N+S) Sodium salt solution containing the following component (N) and component (S)
(N) sodium salt of a monovalent carboxylic acid having a carbon atom number in the range of 2 to 18,
(S) one or more solvents selected from (S1) water and (S2) monohydric saturated alcohols having 1 to 4 carbon atoms
A process of mixing raw materials containing;
Process 2:
A step of removing the solvent (S) of step 1 from the system by heating and/or reduced pressure;
Process 3:
After step 2, the component (a1) and
(a2) General formula (2):
[Tuesday 2]

(In the formula, R each independently represents a monovalent hydrocarbon group having 1 to 9 carbon atoms without an aliphatic unsaturated bond, and a represents a number from 1 to 200),
Organopolysiloxane containing SiH groups at both ends represented by
The above component (N),
(B') the terminal hydrogen is replaced by a hydrocarbon group having 1 to 8 carbon atoms, and the repeating number of the oxyalkylene unit having 2 to 4 carbon atoms, which has a secondary alcoholic hydroxyl group at the other terminal, is in the range of 1 to 3; , one or two or more types of glycol ether compounds characterized by containing no heteroatoms other than oxygen, and
Process of carrying out hydrosilylation reaction in the presence of an effective amount of hydrosilylation reaction catalyst
(However, when the total amount of component (a1), component (a2), and component (B') is 100 parts by weight, the amount of component (B') used is in the range of 40 to 80 parts by weight, and the amount of component (B') is in the range of 40 to 80 parts by weight. The content of sodium cations (Na ⁺ ) in the component (N) is in the range of 3.8 to 43 wt.ppm with respect to the amount used.)
Having,
The following general formula (3):
[Tuesday 3]

(Wherein, R is the same group as above, a, (Represents a divalent hydrocarbon group with 2 to 8 carbon atoms bonded to a polyoxyalkylene block)
A method for producing a composition comprising a polyether-polysiloxane block copolymer (A') having a structural unit represented by in the molecule. The method for producing a composition according to claim 1, wherein steps 1 to 3 are performed in one reaction vessel. The method according to claim 1 or 2, wherein step 1 is a step of mixing one or more types selected from the component (a1), the component (N+S), and other raw material components, In addition, in step 1, the method for producing a composition is a mixing process of raw material components, characterized in that the component (a2) and the hydrosilylation reaction catalyst do not coexist in the raw material system. The method according to any one of claims 1 to 3, wherein component (A') is attached to its molecular chain terminal.
Z ¹ : Alkenyl group, hydroxyl group, alkoxy group or acetoxy group bonded to the polyether moiety; and
Z ² : A monovalent hydrocarbon group, hydroxyl group, alkoxy group, or C1 to C8 hydrocarbon oxyalkylene oxy group that is bonded to a silicon atom and does not have a hetero atom.
A method for producing a composition, which is a polyether-polysiloxane block copolymer having one or more functional groups selected from. The method for producing a composition according to any one of claims 1 to 4, further comprising filtering the composition obtained in step 3 so that the light transmittance (580 nm) is 90% or more. The method according to any one of claims 1 to 5, wherein in the general formulas (2) and (3), a is a number in the range of 10 to 45,
In the above general formulas (1) and (3), y is a number such that the molecular weight of the polyether _portion represented by ( _C A method for producing a composition wherein the average content of ethylene (C ₂ H ₄ O) units is within the range of 30 to 80 mass%. 7. The method according to any one of claims 1 to 6, wherein component (B') is propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol mono. From methyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, tripropylene glycol monopropyl ether, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monoethyl ether A method for producing a composition, which is one or two or more selected glycol ethers. The method according to any one of claims 1 to 7, after step 3,
(C) A step of adding at least one polyether compound that is compatible with the composition containing the components (A') and (B') and selected from the components (C1) to (C3) below, and mixing and homogenizing the composition. (However, the amount of component (C) used is such that the content of component (A') in the finally obtained composition is 1% by weight or more.) A method for producing a composition further comprising.
(C1) polyether monool represented by the following general formula (4)
General formula (4):
[Tuesday 4]

(In the formula, R represents a monovalent hydrocarbon group having 1 to 9 carbon atoms without an aliphatic unsaturated bond, R" represents a methyl group or an ethyl group, k is 0≤k≤20, and l is 4≤l≤50. is satisfied, and the wt.% of the oxyethylene portion of the polyether portion is 60 or less),
(C2) polyether diol represented by the following general formula (5)
General formula (5):
[Tuesday 5]

(In the formula, R" has the same meaning as above, k' satisfies the conditions of 0≤k'≤10, l' satisfies the conditions of 4≤l'≤70, and also represents the wt.% of the oxyethylene portion of the polyether portion. is less than or equal to 30),
(C3) The wt.% of the oxyethylene portion of the polyether portion is 20 or less, the average molecular weight is within the range of 500 to 4500, and is suitable for addition polymerization of alkylene oxide having 2 to 4 carbon atoms to glycerin and/or trimethylolpropane. polyether triol obtained by The method according to any one of claims 1 to 8, wherein at any timing, the antioxidant is added in an amount of 1 to 1000 wt% with respect to 100 parts by mass of the total of the component (A') and (B'). A method for producing a composition further comprising an addition step. (A'') General formula (3'):
[Tuesday 6]

(In the formula, R each independently represents a monovalent hydrocarbon group having 1 to 9 carbon atoms without an aliphatic unsaturated bond, a is a number in the range of 10 to 45, x is a number in the range of 2 to 4, and y is (C _x H _2x O) _y is a number in which the molecular weight of the polyether portion is in the range of 1500 to 5000, and the average content of oxyethylene (C ₂ H ₄ O) units for the entire polyether portion is 30 to 80. It is a number within the range of mass%, the polyether portion contains at least 1 oxypropylene group, n is a number of at least 2, and Y' is connected to an adjacent silicon atom by a carbon-silicon bond and at the same time by an oxygen atom. (Represents a divalent hydrocarbon group with 2 to 8 carbon atoms bonded to a polyoxyalkylene block)
A polyether-polysiloxane block copolymer having a structural unit represented by in the molecule,
(B') the terminal hydrogen is substituted by a hydrocarbon group having 1 to 8 carbon atoms, and the repeating number of the oxyalkylene unit having 2 to 4 carbon atoms, which has a secondary alcoholic hydroxyl group at the other terminal, is in the range of 1 to 3; , one or two or more types of glycol ether compounds characterized by containing no heteroatoms other than oxygen, and
(N) Monovalent carboxylic acid sodium salt with carbon atoms in the range of 2 to 18
, and the mass ratio of component (A''):component (B') is in the range of 20:80 to 60:40, and at the same time, relative to the sum of component (A'') and component (B'), the component A composition containing sodium cations (Na ⁺ ) in (N) in the range of 0.6 to 6.7 wt.ppm. The method of claim 10, further comprising (C) at least one polyester that is compatible with the composition containing the component (A'') and (B') and is selected from the following components (C1) to (C3): A composition containing an ether compound.
(C1) polyether monool represented by the following general formula (4)
General formula (4):
[Tuesday 7]

(In the formula, R represents a monovalent hydrocarbon group having 1 to 9 carbon atoms without an aliphatic unsaturated bond, R" represents a methyl group or an ethyl group, k is 0≤k≤20, and l is 4≤l≤50. is satisfied, and the wt.% of the oxyethylene portion of the polyether portion is 60 or less),
(C2) polyether diol represented by the following general formula (5)
General formula (5):
[Tuesday 8]

(In the formula, R" has the same meaning as above, k' satisfies the conditions of 0≤k'≤10, l' satisfies the conditions of 4≤l'≤70, and also represents the wt.% of the oxyethylene portion of the polyether portion. is less than or equal to 30),
(C3) The wt.% of the oxyethylene portion of the polyether portion is 20 or less, the average molecular weight is within the range of 500 to 4500, and is suitable for addition polymerization of alkylene oxide having 2 to 4 carbon atoms to glycerin and/or trimethylolpropane. polyether triol obtained by A surfactant, a foam stabilizer for polyurethane foam, or a polyurethane composition obtained by the method for producing the composition according to any one of claims 1 to 9 or the composition according to any one of claims 10 to 11. Use as premix liquid for foam. A method for producing a surfactant, a foam stabilizer for polyurethane foam, or a premix solution for polyurethane foam, comprising the method for producing the composition according to any one of claims 1 to 9. A polyurethane foam-forming composition comprising the composition obtained by the method for producing the composition according to any one of claims 1 to 9 or the composition according to any one of claims 10 to 11. A polyurethane foam comprising the composition obtained by the method for producing the composition according to any one of claims 1 to 9 or the composition according to any one of claims 10 to 11 as a raw material.